WO2023114850A2 - Coated fibers comprising a protein polyurethane alloy and methods of making the same - Google Patents
Coated fibers comprising a protein polyurethane alloy and methods of making the same Download PDFInfo
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- WO2023114850A2 WO2023114850A2 PCT/US2022/081563 US2022081563W WO2023114850A2 WO 2023114850 A2 WO2023114850 A2 WO 2023114850A2 US 2022081563 W US2022081563 W US 2022081563W WO 2023114850 A2 WO2023114850 A2 WO 2023114850A2
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- protein
- coating
- coated
- polyurethane
- fiber
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- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229960002591 hydroxyproline Drugs 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 235000021239 milk protein Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 238000012510 peptide mapping method Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000656 polylysine Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000003259 recombinant expression Methods 0.000 description 1
- 238000007753 roll-to-roll coating process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003307 slaughter Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 108010013480 succinylated gelatin Proteins 0.000 description 1
- 229940007079 succinylated gelatin Drugs 0.000 description 1
- 238000010613 succinylation reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- FGMPLJWBKKVCDB-UHFFFAOYSA-N trans-L-hydroxy-proline Natural products ON1CCCC1C(O)=O FGMPLJWBKKVCDB-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/40—Yarns in which fibres are united by adhesives; Impregnated yarns or threads
- D02G3/404—Yarns or threads coated with polymeric solutions
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/15—Proteins or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
- D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/16—Processes for the non-uniform application of treating agents, e.g. one-sided treatment; Differential treatment
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/46—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing natural macromolecular substances or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/06—Material containing basic nitrogen containing amide groups using acid dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/10—Material containing basic nitrogen containing amide groups using reactive dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/241—Polyamides; Polyurethanes using acid dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/248—Polyamides; Polyurethanes using reactive dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/82—Textiles which contain different kinds of fibres
- D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
- D06P3/8214—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing ester and amide groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/82—Textiles which contain different kinds of fibres
- D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
- D06P3/8219—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and amide groups
Definitions
- This disclosure relates to fibers coated with a coating comprising a protein polyurethane alloy, the protein polyurethane alloy comprising one or more proteins dissolved in a polyurethane.
- the fibers can be used to make a textile or fabric article, for example, a textile or fabric article previously prepared from natural leather.
- leather is a versatile product used across many industries, including the furniture industry, where leather is regularly used as upholstery, the clothing industry, where leather is used to manufacture pants and jackets, the shoe industry, where leather is used to prepare casual and dress shoes, the luggage industry, the handbag and accessory industry, and in the automotive industry.
- the global trade value for leather is high, and there is a continuing and increasing demand for leather products.
- natural leathers are produced from animal skins, and as such, requires raising and slaughtering livestock. Raising livestock requires enormous amounts of feed, pastureland, water, and fossil fuels and contributes to air and waterway pollution, through, for example, greenhouse gases like methane.
- the present disclosure provides fibers coated with a protein polyurethane alloy and suitable for use in a variety of applications, including textile and fabric applications.
- a first embodiment (1) of the present disclosure is directed to a coated fiber comprising a core fiber and a coating disposed over the core fiber, the coating comprising a protein dissolved within a polyurethane.
- the protein of the first embodiment (1) is a soy protein.
- the soy protein of the second embodiment (2) is soy protein isolate.
- the coated fiber of any one of embodiments (1) - (3) further comprises a dye.
- the coating of the coated fiber of the fourth embodiment (4) comprises the dye.
- the coated fiber of any one of embodiments (1) - (5) has a coating uptake of greater than or equal to about 10%.
- the coated fiber of any one of embodiments (1) - (5) has a coating uptake ranging from about 10% to about 100%.
- the coating of any one of embodiments (1) - (7) has a thickness of greater than or equal to about 100 nanometers.
- the coating of any one of embodiments (1) - (7) has a thickness ranging from about 100 nanometers to about 1 millimeter.
- the coating of any one of embodiments (1) - (9) has a thickness greater than or equal to 1% of an effective diameter of the core fiber.
- the coating of any one of embodiments (1) - (10) comprises about 5 wt% to about 50 wt% of the protein and about 50 wt% to about 95 wt% of the polyurethane.
- the protein of any one of embodiments (1) or (4) - (11) is an enzyme.
- the protein of any one of embodiments (1) or (4) - (11) is selected from the group consisting of: soy protein, collagen, gelatin, bovine serum albumin, pea protein, egg white albumin, casein protein, peanut protein, edestin protein, whey protein, karanja protein, hemp protein, an enzyme, and cellulase.
- a fourteenth embodiment (14) is directed to a method of making a coated fiber, the method comprising coating a core fiber with a coating comprising a protein dissolved within a polyurethane.
- coating the core fiber according to the fourteenth embodiment (14) comprises a dip coating process.
- the method of the fourteenth embodiment (14) or the fifteenth embodiment (15) further comprises dying the coating.
- the coating of the sixteenth embodiment (16) is dyed after the coating is coated on the core fiber.
- the coating of the sixteenth embodiment (16) is dyed before the coating is coated on the core fiber.
- a nineteenth embodiment (19) is directed to a material comprising a plurality of the coated fibers according to any one of embodiments (1) - (13), wherein a first coated fiber is in contact with a second coated fiber, and wherein the first and second coated fibers can slide over each other.
- the material of the nineteenth embodiment (19) further comprises a fiber not coated with a protein dissolved within a polyurethane, wherein the first coated fiber is in contact with the fiber not coated with a protein dissolved within a polyurethane, and wherein the first coated fiber and the fiber not coated with a protein dissolved within a polyurethane can slide over each other.
- the amount of the coating disposed on the coated fibers within the material of the nineteenth embodiment (19) is uniform through a cross-sectional thickness of the material such that all the coated fibers within the material have a coating uptake that is substantially the same.
- FIG. 1 illustrates a coated fiber according to some embodiments.
- FIG. 2 illustrates a coated fiber having a star-shaped core fiber according to some embodiments.
- FIGs. 3-5 illustrate coated fibers including discontinuous coatings according to some embodiments.
- FIGs. 6 and 7 illustrate partially coated fibers according to some embodiments.
- the term “comprising” is an open-ended transitional phrase.
- a list of elements following the transitional phrase “comprising” is a non-exclusive list, such that elements in addition to those specifically recited in the list can also be present.
- the phrase “consisting essentially of’ limits the composition of a component to the specified materials and those that do not materially affect the basic and novel characteristic(s) of the component.
- the phrase “consisting of’ limits the composition of a component to the specified materials and excludes any material not specified.
- the term “about” refers to a value that is within ⁇ 10% of the value stated.
- about 3 MPa can include any number ranging from 2.7 MPa to 3.3 MPa.
- the phrase “disposed on” means that a first component (e.g., a coating) is in direct contact with a second component.
- a first component “disposed on” a second component can be deposited, formed, placed, or otherwise applied directly onto the second component. In other words, if a first component is disposed on a second component, there are no components between the first component and the second component.
- the phrase “disposed over” means other components (e.g., layers or substrates) may or may not be present between a first component and a second component.
- a “bio-based polyurethane” is a polyurethane where the building blocks of polyols, such as diols and diacids like succinic acid, are derived from a biological material such as corn starch.
- the term “substantially free of’ means that a component is present in a detectable amount not exceeding about 0.1 wt%.
- the term “free of’ means that a component is not present in a blend or material (e.g., a protein polyurethane alloy), even in trace amounts.
- a “fiber” refers to a construct having a length that is substantially larger than its effective diameter.
- a “fiber” may be a filament, a thread, a yarn (for example, a knitted or woven yam), a cable, a cord, a fiber tow, a tape, a ribbon, a monofilament, a braid, a string, or any other form of material that can be spooled.
- a fiber can have a length that is at least two times larger than its effective diameter.
- a fiber can have a length that is at least ten times larger than its effective diameter.
- a fiber can have a length that is at least 100 times larger than its effective diameter.
- a fiber can have a length that is at least 200 times larger than its effective diameter. In some embodiments, a fiber can have a length that is at least 300 times larger than its effective diameter. In some embodiments, a fiber can have a length that is at least 500 times larger than its effective diameter.
- an “effective diameter” is used herein to describe the diameter of a fiber, but this term should not be interpreted as requiring a fiber to have a circular diameter or shape. Instead, a fiber can have a non-circular shape, and in such embodiments, the term “effective diameter” is intended to refer to the maximum cross-sectional dimension of the shape.
- the “effective diameter” of a fiber having an elliptical cross-sectional shape would be the length of the major axis of the elliptical shape.
- the effective diameter is the largest effective diameter.
- collagen refers to the family of at least 28 distinct naturally occurring collagen types including, but not limited to collagen types I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, and XX.
- the term collagen as used herein also refers to collagen prepared using recombinant techniques.
- the term collagen includes collagen, collagen fragments, collagen-like proteins, triple helical collagen, alpha chains, monomers, gelatin, trimers and combinations thereof.
- collagen and collagen-like proteins are known in the art (see, e.g., Bell, EP 1232182B1, Bovine collagen and method for producing recombinant gelatin; Olsen, et al., U.S. Patent No. 6,428,978 and VanHeerde, et al., U.S. Patent No. 8,188,230, incorporated by reference herein in their entireties)
- collagen of any type whether naturally occurring or prepared using recombinant techniques, can be used in any of the embodiments described herein. That said, in some embodiments, the collagen described herein can be prepared using bovine Type I collagen.
- Collagens are characterized by a repeating triplet of amino acids, -(Gly-X-Y)n-, so that approximately one-third of the amino acid residues in collagen are glycine. X is often proline and Y is often hydroxyproline. Thus, the structure of collagen may consist of three intertwined peptide chains of differing lengths. Different animals may produce different amino acid compositions of the collagen, which may result in different properties (and differences in the resulting leather). [0044] Any type of collagen, truncated collagen, unmodified or post-translationally modified, or amino acid sequence-modified collagen can be used as part of the protein polyurethane alloy.
- the collagen can be plant-based collagen.
- the collagen can be a plant-based collagen made by CollPlant.
- a collagen solution can be fibrillated into collagen fibrils.
- collagen fibrils refer to nanofibers composed of tropocollagen or tropocollagen-like structures (which have a triple helical structure).
- triple helical collagen can be fibrillated to form nanofibrils of collagen.
- a recombinant collagen can comprise a collagen fragment of the amino acid sequence of a native collagen molecule capable of forming tropocollagen (trimeric collagen).
- a recombinant collagen can also comprise a modified collagen or truncated collagen having an amino acid sequence at least 70, 80, 90, 95, 96, 97, 98, or 99% identical or similar to a native collagen amino acid sequence (or to a fibril forming region thereof or to a segment substantially comprising [Gly-X-Y]n).
- the collagen fragment can be a 50 kDa portion of a native collagen.
- Native collagen sequences include the amino acid sequences of CollAl, CollA2, and Col3 Al, described by Accession Nos.
- the collagen fragment can be a portion of human collagen alpha-l(III) (Col3Al; Uniprot # P02461, Entrez Gene ID # 1281). In some embodiments, the collagen fragment can comprise the amino acid sequence listed as SEQ ID NO: 1.
- Coated fibers described herein comprise a core fiber coated with a coating comprising a protein polyurethane alloy.
- the protein polyurethane alloys described herein comprise a protein dissolved within a polyurethane, or a plurality of polyurethanes.
- the protein polyurethane alloys described herein can comprise a protein that is miscible with only one of a plurality of phases of the polyurethane, or the plurality of polyurethanes, with which it is blended.
- the protein polyurethane alloy can include a protein that is miscible with only the hard phase of the polyurethane, or the plurality of polyurethanes, having both a hard phase and a soft phase.
- Protein polyurethane alloys described herein can be free of or substantially free of protein in form of particles dispersed in a polyurethane.
- the protein polyurethane alloys can be free of or substantially free of protein particles having an average diameter of greater than 1 micron (pm).
- the protein polyurethane alloys can be free of or substantially free of soy protein particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of or substantially free of collagen particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of or substantially free of gelatin particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of or substantially free of bovine serum albumin particles having an average diameter of greater than 1 micron (pm).
- the protein polyurethane alloys can be free of or substantially free of pea protein particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of or substantially free of egg white albumin particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of or substantially free of casein protein particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of or substantially free of peanut protein particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of or substantially free of edestin protein particles having an average diameter of greater than 1 micron (pm).
- the protein polyurethane alloys can be free of or substantially free of whey protein particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of or substantially free of karanja protein particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of, or substantially free of, cellulase particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of, or substantially free of, recombinant collagen fragment particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of, or substantially free of, hemp protein particles having an average diameter of greater than 1 micron (pm).
- the proteins for use in coatings comprising a protein polyurethane alloy can be succinylated proteins.
- a succinylated protein is a protein modified with the addition of a succinyl group to a side chain of an amino acid in the protein. Most commonly, the succinyl group is added to lysine side chains.
- the method of adding a succinyl group to a side chain of an amino acid in a protein is commonly referred to as protein succinylation. Addition of succinyl groups on a protein can alter the protein’s functional and structural properties. In some cases, the addition of a relatively large modification like a succinyl moiety can be expected to alter the tertiary structure of the protein.
- a lysine side chain can be altered from a primary amine to an acid, making it more hydrophilic, and can change its charge from positive to negative in physiological pH. Succinylation can be accomplished using techniques and chemistry well known the art.
- a succinylated protein for use in the polyurethane alloys disclosed herein can be a protein containing lysine.
- the succinylated protein can be a succinylated soy protein.
- the succinylated protein can be a succinylated soy protein isolate.
- the succinylated protein can be a succinylated collagen.
- the succinylated protein can be a succinylated gelatin.
- the succinylated protein can be succinylated bovine serum albumin.
- the succinylated protein can be a succinylated pea protein.
- the succinylated protein can be succinylated egg white albumin. In some embodiments, the succinylated protein can be a succinylated casein protein. In some embodiments, the succinylated protein can be a succinylated peanut protein. In some embodiments, the succinylated protein can be a succinylated edestin protein. In some embodiments, the succinylated protein can be a succinylated whey protein. In some embodiments, the succinylated protein can be a succinylated karanja protein. In some embodiments, the succinylated protein can be a succinylated cellulase. In some embodiments, the succinylated protein can be a succinylated hemp protein.
- the succinylated protein can have a solubility in water, measured as described below, of about 50% to about 100%, including subranges.
- the succinylated protein can have a solubility in water of about 50% to about 100%, about 51% to about 100%, about 52% to about 100%, about 53% to about 100%, about 54% to about 100%, about 55% to about 100%, about 56% to about 100%, about 57% to about 100%, about 58% to about 100%, about 59% to about 100%, about 60% to about 100%, about 61% to about 100%, about 62% to about 100%, about 63% to about 100%, about 64% to about 100%, about 65% to about 100%, about 66% to about 100%, about 67% to about 100%, about 68% to about 100%, about 69% to about 100%, about 70% to about 100%, about 71% to about 100%, about 72% to about 100%, about 73% to about 100%, about 74% to about 100%, about 75% to about 100%, about 76% to about 100%, about
- the succinylated protein can have a solubility in water of about 60% to about 90%, 61% to about 90%, about 62% to about 90%, about 63% to about 90%, about 64% to about 90%, about 65% to about 90%, about 66% to about 90%, about 67% to about 90%, about 68% to about 90%, about 69% to about 90%, about 70% to about 90%, about 71% to about 90%, about 72% to about 90%, about 73% to about 90%, about 74% to about 90%, about 75% to about 90%, about 76% to about 90%, about 77% to about 90%, about 78% to about 90%, about 79% to about 90%, about 80% to about 90%, about 81% to about 90%, about 82% to about 90%, about 83% to about 90%, about 84% to about 90%, or about 85% to about 90%.
- the succinylated protein can have a solubility in water of about 50%, about 51%, about 52%, about 53%, about 54%, about 55%, about 56%, about 57%, about 58%, about 59%, about 60%, about 61%, about 62%, about 63%, about 64%, about 65%, about 66%, about 67%, about 68%, about 69%, about 70%, about 71%, about 72%, about 73%, about 74%, about 75%, about 76%, about 77%, about 78%, about 79%, about 80%, about 81%, about 82%, about 83%, about 84%, about 85%, about 86%, about 87%, about 88%, about 89%, about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%, about 97%, about 98%, about 99%, or about 100%.
- solubility of a protein in water is measured according to the following method.
- the succinylated protein is suspended to a 5% (w/v) aqueous solution with DI water and the total solids are measured with a moisture analyzer.
- 35 mL of the 5% solution is centrifuged in a 50 mL tube for 10 minutes at 15,000 x g (times gravity). After centrifugation, the supernatant is decanted and the volume and total solids of the supernatant (soluble fraction) is measured.
- the succinylated protein can have an average lysine modification, measured as specified below, of about 20% to about 100%, including subranges.
- the succinylated protein can have an average lysine modification of about 20% to about 100%, about 22% to about 100%, about 24% to about 100%, about 25% to about 100%, about 26% to about 100%, about 28% to about 100%, about 30% to about 100%, about 32% to about 100%, about 34% to about 100%, about 35% to about 100%, about 36% to about 100%, about 38% to about 100%, about 40% to about 100%, about 42% to about 100%, about 44% to about 100%, about 45% to about 100%, about 46% to about 100%, about 48% to about 100%, about 50 % to about 100%, about 52% to about 100%, about 54% to about 100%, about 55% to about 100%, about 56% to about 100%, about 58% to about 100%, about 60% to about 100%, about 62% to about 100%, about 64% to about 100%, about %
- the succinylated protein can have an average lysine modification of about 60% to about 90%, about 62% to about 90%, about 64% to about 90%, about 65% to about 90%, about 66% to about 90%, about 68% to about 90%, about 70% to about 90%, about 72% to about 90%, about 74% to about 90%, about 75% to about 90%, about 76% to about 90%, about 78% to about 90%, about 80% to about 90%, about 82% to about 90%, about 84% to about 90%, or about 85% to about 90%.
- the succinylated protein can have an average lysine modification of about 60% to about 80%, about 62% to about 80%, about 64% to about 80%, about 65% to about 80%, about 66% to about 80%, about 68% to about 80%, about 70% to about 80%, about 72% to about 80%, about 74% to about 80%, or about 75% to about 80%.
- the succinylated protein can have an average lysine modification of about 20%, about 21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27%, about 28%, about 29%, about 30%, about 31%, about 32%, about 33%, about 34%, about 35%, about 36%, about 37%, about 38%, about 39%, about 40%, about 41%, about 42%, about 43%, about 44%, about 45%, about 46%, about 47%, about 48%, about 49%, about 50%, about 51%, about 52%, about 53%, about 54%, about 55%, about 56%, about 57%, about 58%, about 59%, about 60%, about 61%, about 62%, about 63%, about 64%, about 65%, about 66%, about 67%, about 68%, about 69%, about 70%, about 71%, about 72%, about 73%, about 74%, about 75%, about 76%, about 77%, about 78%
- the average lysine modification for a succinylated protein disclosed herein is measured using the following lysine modification assay.
- a protein sample is digested using trypsin and loaded onto a liquid chromatography-mass spectrometer (LC/MS). After running the sample on the LC/MS, the sample is mapped by matching the digested peptides against the reference protein sequence for Beta- conglycinin alpha’ subunit (Gene CG-1; Organism: Glycine max (soybean) (Glycine hispida), which contains the possibility for both modified and unmodified lysine residues.
- a protein for use in the protein polyurethane alloys disclosed herein can be a protein containing lysine.
- the protein can be a soy protein.
- the protein can be soy protein isolate.
- the protein can be a collagen.
- the protein can be gelatin.
- the protein can be bovine serum albumin.
- the protein can be pea protein.
- the protein can be egg white albumin.
- the protein can be casein protein.
- the protein can be peanut protein.
- the protein can be edestin protein.
- the protein can be whey protein.
- the protein can be karanja protein.
- the protein can be hemp protein.
- the protein can be an enzyme.
- the protein can be cellulase.
- Suitable polyurethanes for use in the coatings comprising the protein polyurethane alloy described herein include those that comprise at least two phases including a “soft phase” and a “hard phase.”
- the soft phase is formed from polyol segments within the polyurethane that separate from the urethane-containing phase due to differences in polarity.
- the urethane-containing phase is referred to as the hard phase. This phase separation is well known in the art and is the basis of the many of the properties of polyurethanes.
- the soft phase is typically elastomeric at room temperature, and typically has a softening point or glass transition temperature (Tg) below room temperature.
- Tg can be measured by Dynamic Mechanical Analysis (DMA) and quantified by either the peak of tan(6) or the onset of the drop in storage modulus. Alternately, Tg can be measured by Differential Scanning Calorimetry (DSC). In some cases, there can be crystallinity in the soft phase, which can be seen as a melting point, typically between 0 °C and about 60 °C.
- the hard phase typically has a Tg or melting point above room temperature, more typically above about 80 °C.
- the softening of the hard phase can be measured by measuring the onset of the drop in storage modulus (sometimes referred to as stiffness) as measured by DMA.
- the “soft phase” for the polyurethane or the protein polyurethane alloy including the polyurethane comprises the polyol component of the polyurethane. Its function is to be soft and flexible at temperatures above its Tg to lend toughness, elongation, and flexibility to the polyurethane.
- Typical soft segments can comprise polyether polyols, polyester polyols, polycarbonate polyols, and mixtures thereof.
- the soft segments typically range in molecular weight from about 250 D to greater than about 5 kD.
- the “hard phase” for the polyurethane or the protein polyurethane alloy including the polyurethane comprises the urethane segments of the polymer that are imparted by the isocyanate(s) used to connect the polyols along with short chain diols such as butane diol, propane diol, and the like.
- Typical isocyanates useful for the present polyurethanes include, but are not limited to, hexamethylene diisocyanate, isophorone diisocyanate, methylene diisocyanate, phenyl diisocyanate, and the like.
- the hard segment is stiffer and has a higher softening point compared to the soft segment.
- the function of the hard phase is to provide, among other properties, strength, temperature resistance, and abrasion resistance to the polyurethane.
- the protein can be miscible with only the hard phase, leaving soft phase transitions substantially unaltered. Without wishing to be bound by particular theory, it is believed that when the protein is dissolved in the hard phase, it significantly increases the temperature at which the hard phase begins to soften, thus increasing the temperature resistance of the alloy.
- the one or more proteins can be dissolved within the hard phase of the one or more polyurethanes.
- the protein polyurethane alloy can include at least one protein miscible with the hard phase of one or more polyurethanes in the alloy.
- the protein polyurethane alloy can include a plurality of proteins and/or a plurality of polyurethane hard phases that are miscible with each other.
- the protein, or plurality of proteins is believed to be dissolved in the hard phase of the polyurethane, or plurality of polyurethanes.
- the protein polyurethane alloy can include a plurality of proteins dissolved within or more polyurethanes such that the proteins and the polyurethane(s) form a homogenous mixture when blended and dried.
- the protein polyurethane alloy including a homogenous mixture of protein and polyurethane does not include a substantial amount of protein not dissolved in the polyurethane. That said, and in some embodiments, the protein polyurethane alloy can include a fraction of protein dispersed within the polyurethane.
- the protein polyurethane alloy can be transparent.
- a transparent protein polyurethane alloy can indicate that the protein is miscible with the hard phase of the polyurethane in the alloy.
- a “transparent” material means material having an opacity of about 50% or less. Opacity is measured by placing a sample of material over a white background to measure the Y tristimulus value (“Over white Y”) in reflectance with a spectrometer using the D65 10 degree illuminant. The same sample is then placed over a black background and the measurement is repeated, yielding “Over black Y”. Percent opacity is calculated as “Over black Y” divided by “Over white Y” times 100. 100% opacity is defined as lowest transparency and 0% opacity is defined as the highest transparency.
- the protein polyurethane alloy can be transparent and can have an opacity ranging from 0% to about 50%, including subranges.
- the transparent protein polyurethane alloy can have an opacity ranging from 0% to about 40%, 0% to about 30%, 0% to about 20%, 0% to about 10%, or 0% to about 5%.
- the transparency of the protein polyurethane alloy is evaluated before dying or otherwise coloring the protein polyurethane alloy.
- a transparent protein polyurethane alloy can be created by selecting and blending the appropriate combination of one or more proteins and one or more polyurethanes. While not all combinations of protein and polyurethane will result in a transparent protein polyurethane alloy, it is within the skill of the ordinarily skilled artisan to identify whether a given blend results in a transparent protein polyurethane alloy in view of this disclosure.
- the transparent protein polyurethane alloy can provide unique characteristics for the coated fiber. For example, compared to a nontransparent coating, the transparent protein polyurethane alloy can provide unique depth of color when dyed.
- the protein polyurethane alloy can include one or more coloring agents.
- the coloring agent can be a colored dye, for example a fiber reactive dye, a direct dye, an acid dye, or a natural dye.
- Exemplary dyes include but are not limited to, Azo structure acid dyes, metal complex structure acid dyes, anthraquinone structure acid dyes, and azo/diazo direct dyes.
- the coloring agent can be pigment, for example a lake pigment.
- Suitable polyurethanes include, but are not limited to, aliphatic polyurethanes, aromatic polyurethanes, bio-based polyurethanes, or acrylic acid modified polyurethanes. Suitable polyurethanes are commercially available from manufacturers including Lubrizol, Hauthaway, Stahl, and the like.
- a polyurethane for a protein polyurethane alloy can be bio-polyurethane.
- the polyurethane is a water-dispersible polyurethane.
- the polyurethane can be a polyester polyurethane.
- the polyurethane can be a polyether polyurethane.
- the polyurethane can be a polycarbonate-based polyurethane. In some embodiments, the polyurethane can be an aliphatic polyester polyurethane. In some embodiments, the polyurethane can be an aliphatic polyether polyurethane. In some embodiments, the polyurethane can be an aliphatic polycarbonate polyurethane. In some embodiments, the polyurethane can be an aromatic polyester polyurethane. In some embodiments, the polyurethane can be an aromatic polyether polyurethane. In some embodiments, the polyurethane can be an aromatic polycarbonate polyurethane.
- the polyurethane can have a soft segment selected from the group consisting of: polyether polyols, polyester polyols, polycarbonate polyols, and mixtures thereof.
- the polyurethane can have a hard segment comprising diisocyanates and optionally short chain diols. Suitable diisocyanates can be selected from the group consisting of: aliphatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate; aromatic diisocyanates such as 4,4’ diphenyl methylene diisocyanate, toluene diisocyanate, phenyl diisocyanate, and mixtures thereof.
- Suitable short chain diols include ethylene glycol, propane diol, butane diol, 2,2 methyl 1,3 propane diol, pentane diol, hexane diol and mixtures thereof.
- crosslinkers such as multifunctional alcohols, for example, trimethylol propane triol, or diamines such as ethylene diamine or 4,4’diamino, diphenyl diamine.
- Exemplary commercial polyurethanes include but are not limited to L3360 and Hauthane HD-2001 available from C.L.
- L3360 is a aliphatic polyester polyurethane polymer aqueous dispersion having a 35% solids content, a viscosity of 50 to 500 cps (centipoise), and a density of about 8.5 Ib/gal (pounds per gallon).
- HD-2001 is an aliphatic polyester polyurethane polymer aqueous dispersion having a 40% solids content, a viscosity of 50 to 500 cps, and a density of about 8.9 Ib/gal.
- BONDTHANETM UD-108 is an aliphatic polyether polyurethane polymer aqueous dispersion having a 33% solids content, a viscosity of 300 cps, and a density of 8.7 Ib/gal.
- BONDTHANETM UD-250 is an aliphatic polyester polyurethane polymer aqueous dispersion having a 35% solids content, a viscosity of 200 cps, and a density of 8.8 Ib/gal.
- BONDTHANETM UD-303 is an aliphatic poly ether polyurethane polymer aqueous dispersion having a 35% solids content, a viscosity of less than 500 cps, and a density of 8.7 Ib/gal.
- EPTOAL® P100 ECO is a polyester polyurethane elastomer aqueous dispersion having approximately 40% solids and a viscosity of about 40 mPas.
- RC-2214 is an aliphatic polyether polyurethane polymer aqueous dispersion having a 58-60% solids content, a viscosity of 4,000 to 15,000 cps, and a density of about 8.9 Ib/gal.
- Exemplary bio-based polyurethanes include, but are not limited to, L3360 available from C.L. Hauthaway & Sons Corporation, IMPRANIL® Eco DLS, IMPRANIL® Eco DL 519, IMPRANIL® Eco DLP-R, and IMPRAPERM® DL 5249 available from Covestro.
- IMPRANIL® Eco DLS is an anionic, aliphatic polyester polyurethane polymer aqueous dispersion having approximately 50% solids content, a viscosity of less than 1,200 MPa s, and a density of about 1.1 g/cc.
- IMPRANIL® Eco DL 519 is an anionic, aliphatic polyester polyurethane polymer aqueous dispersion.
- IMPRANIL® Eco DLP-R is an anionic, aliphatic polyester polyurethane polymer aqueous dispersion.
- IMPRAPERM® DL 5249 is an anionic aliphatic polyester-polyurethane polymer aqueous dispersion.
- the polyurethane can include reactive groups that can be cross-linked with a protein.
- exemplary reactive groups include, but are not limited to, a sulfonate, an aldehyde, a carboxylic acid or ester, a blocked isocyanate, or the like, and combinations thereof.
- the polyurethane can be crosslinked to the protein in the protein polyurethane alloy through the reaction of a reactive group on the protein with the reactive group present in the polyurethane.
- Suitable proteins include, but are not limited to, collagen, gelatin, bovine serum albumin (BSA), soy proteins, pea protein, egg white albumin, casein, peanut protein, edestin protein, whey protein, karanja protein, cellulase, and hemp.
- Suitable collagens include, but are not limited to, recombinant collagen (r-Collagen), a recombinant collagen fragment, and extracted collagens.
- Suitable soy proteins include, but are not limited to, soy protein isolate (SPI), soymeal protein, and soy protein derivatives.
- the soy protein isolate can be partially hydrolyzed soy protein isolate.
- Suitable pea proteins include, but are not limited to, pea protein isolate, and pea protein derivatives.
- the pea protein isolate can be partially hydrolyzed pea protein isolate.
- the gelatin is gelatin from porcine skin, Type A (Sigma Aldrich G2500).
- the collagen is extracted bovine collagen purchased from Wuxi BIOT Biology-technology Company.
- the r-Collagen is recombinant collagen from Modem Meadow.
- the soy protein isolate is soy protein isolate purchased from MP Medicals (IC90545625).
- the pea protein is pea protein powder purchased from Bobs Red Mills (MTX5232).
- the egg white albumin protein is albumin from chicken egg white (Sigma Aldrich A5253).
- the casein protein is casein from bovine milk (Sigma Aldrich C7078).
- the peanut protein is peanut protein powder purchased from Tru-Nut.
- the whey protein is whey from bovine milk (Sigma Aldrich W1500).
- suitable soy protein isolates include, but are not limited to, soy protein isolate purchased from AMD (Clarisoy 100, 110, 150, 170, 180), or DuPont (SUPRO® XT 55, SUPRO® XT 221D, SUPRO® XT 221D-IP, and SOB IND® Balance).
- Other suitable pea protein powders include, but are not limited to, pea protein powder purchased from Puris (870 and 870H).
- Karanja protein is a protein found in Karanja seeds harvested from Pongamia pinnata trees (also known as Pongamia glabra trees). See Rahman, M., and Netravali, “Green Resin from Forestry Waste Residue ‘Karanja (Pongamia pinnata) Seed Cake’ for Biobased Composite Structures,” ACS Sustainable Chem. Eng., 2: 2318-2328 (2014); see also Mandal et al., “Nutritional Evaluation of Proteins from three Non-traditional Seeds with or without Amino Acids Supplementation in Albino Rats,” Proc. Indian natn. Sci. Acad., B50, No. 1, 48-56 (1984).
- the protein can be extracted from Karanja seeds using a solvent extraction process.
- the karanja protein can be karanja protein isolate.
- karanja protein isolate can be obtained by alkaline extraction and acid precipitation of defatted karanja seed cake. See Rahman, M., and Netravali, “Green Resin from Forestry Waste Residue ‘Karanja (Pongamia pinnata) Seed Cake’ for Biobased Composite Structures,” ACS Sustainable Chem. Eng., 2: 2318-2328 (2014).
- Cellulase-RG Native Trichoderma sp. Cellulase available from CREATIVE ENZYMES®.
- Cellulase-IG laboratory grade cellulase available from Carolina Biological Supply Company.
- the 50 KDa recombinant collagen fragment (50 KDa r-Collagen fragment) in Table 1 is a collagen fragment comprising the amino acid sequence listed as SEQ ID NO: 1.
- the “dissolution method” listed in Table 1 is an exemplary aqueous solvent in which the protein can be dissolved in a solution that is miscible with the hard phase of the polyurethane as described herein. Proteins that can be at least partly dissolved in an aqueous solution are suitable for forming protein polyurethane alloys with polyurethane dispersions.
- the protein can have one or more of the following properties: (i) a molecular weight within a range described herein (ii) an isoelectric point within a range described below, (iii) an amino acid composition measured in grams of lysine per 100 grams of protein in a range described below, and (iv) protein thermostability up to 200 °C.
- the protein suitable for blending with the polyurethane can have a molecular weight ranging from about 1 KDa to about 700 KDa, including subranges.
- the protein can have a molecular weight ranging from about 1 KDa to about 700 KDa, about 10 KDa to about 700 KDa, about 20 KDa to about 700 KDa, about 50 KDa to about 700 KDa, about 100 KDa to about 700 KDa, about 200 KDa to about 700 KDa, about 300 KDa to about 700 KDa, about 400 KDa to about 700 KDa, about 500 KDa to about 700 KDa, about 600 KDa to about 700 KDa, about 1 KDa to about 600 KDa, about 1 KDa to about 500 KDa, about 1 KDa to about 400 KDa, about 1 KDa to about 300 KDa, about 1 KDA to about 200 KDa, about 1 KDa to about 100 KDa
- the protein suitable for blending with the polyurethane can have an isoelectric point ranging from about 4 to about 10, including subranges.
- the protein can have an isoelectric point ranging from about 4 to about 10, about 4.5 to about 9.5, about 5 to about 9, about 5.5 to about 8.5, about 6 to about 8, about 6.5 to about 7.5, or about 6.5 to about 7, or within a range having any two of these values as endpoints, inclusive of the endpoints.
- the protein can have an isoelectric point ranging from about 4 to about 5.
- the protein suitable for blending with the polyurethane can have an amino acid composition measured in grams of lysine per 100 grams of protein (as referred to as a “lysine weight percent”) ranging from about 0.5 wt% to about 100 wt%, including subranges.
- the protein can have a lysine weight percent ranging from about 0.5 wt% to about 100 wt%, about 1 wt% to about 100 wt%, about 5 wt% to about 100 wt%, about 10 wt% to about 100 wt%, about 20 wt% to about 100 wt%, about 30 wt% to about 100 wt%, about 40 wt% to about 100 wt%, about 50 wt% to about 100 wt%, about 60 wt% to about 100 wt%, about 70 wt% to about 100 wt%, about 80 wt% to about 100 wt%, or about 90 wt% to about 100 wt%, or within a range having any two of these values as endpoints, inclusive of the endpoints.
- the protein can be a polylysine.
- the protein suitable for blending with the polyurethane can have a lysine weight percent ranging from about 0.5 wt% to about 20 wt%, including subranges.
- the protein can have a lysine weight percent ranging from about 0.5 wt% to about 20 wt%, about 1 wt% to about 19 wt%, about 2 wt% to about 18 wt%, about 3 wt% to about 17 wt%, about 4 wt% to about 16 wt%, about 5 wt% to about 15 wt%, about 6 wt% to about 14 wt%, about 7 wt% to about 13 wt%, about 8 wt% to about 12 wt%, about 9 wt% to about 11 wt%, or about 9 wt% to about 10 wt%, or within a range having any two of these values as endpoints, inclusive of the endpoints.
- the protein can have a lysine weight percent ranging from about 1 wt% to about 20 wt%. In some embodiments, the protein can have a lysine weight percent ranging from about 5 wt% to about 20 wt%. In some embodiments, the protein can have a lysine weight percent ranging from about 1 wt% to about 12 wt%. In some embodiments, the protein can have a lysine weight percent ranging from about 5 wt% to about 12 wt%. In some embodiments, the protein can have a lysine weight percent ranging from about 1 wt% to about 15 wt%. In some embodiments, the protein can have a lysine weight percent ranging from about 5 wt% to about 15 wt%.
- the protein suitable for blending with the polyurethane can be thermo-stable.
- the protein can be non-thermo-stable.
- protein thermo-stability is determined by a differential scanning calorimetry (DSC), where a pre-dried protein powder (with moisture less than 3%) is scanned from 0 °C to 200 °C.
- DSC differential scanning calorimetry
- an endothermic peak larger than 10 mW/mg is determined to be a “denaturation peak”, and the temperature corresponding to the endothermic “denaturation peak” is defined as the “denaturation temperature” of the protein.
- a protein that is “thermo-stable” means that the protein has denaturation temperature of 200 °C or more.
- a protein with a denaturation temperature below 200 °C is considered “non-thermo-stable.”
- one or more proteins before blending with one or more polyurethanes, can be dissolved in an aqueous solution to form an aqueous protein mixture.
- dissolving the protein in an aqueous solution before blending the protein with one or more polyurethanes can facilitate miscibility of the protein with the hard phase of the one or more polyurethanes.
- dissolving the protein in an aqueous solution before blending the protein with one or more polyurethanes can facilitate miscibility of the protein with the hard phase of the polyurethane(s). Not all proteins are naturally miscible with any phase of a polyurethane.
- Suitable aqueous solutions include, but are not limited to, water, an aqueous alkali solution, an aqueous acid solution, an aqueous solution including an organic solvent, a urea solution, and mixtures thereof.
- the aqueous alkali solution can be a basic solution such as a sodium hydroxide, ammonia or ammonium hydroxide solution.
- examples of an acidic aqueous solution can be an acetic acid or hydrochloric acid (HC1) solutions.
- Suitable organic solvents include, but are not limited to, ethanol, isopropanol, acetone, ethyl acetate, isopropyl acetate, glycerol, and the like.
- the protein concentration in the aqueous protein mixture can range from about 10 g/L to about 300 g/L, including subranges.
- the amount of protein in the protein polyurethane alloy can range from about 5 wt% to about 50 wt% of protein, including subranges.
- the amount of protein in the polyurethane alloy can range from about 5 wt% to about 50 wt%, about 10 wt% to about 50 wt%, about 15 wt% to about 50 wt%, about 20 wt% to about 50 wt%, about 25 wt% to about 50 wt%, about 30 wt% to about 50 wt%, about 35 wt% to about 50 wt%, about 40 wt% to about 50 wt%, about 45 wt% to about 50 wt%, about 5 wt% to about 45 wt%, about 5 wt% to about 40 wt%, about 5 wt% to about 35 wt%, about 5 wt% to about 30 wt%, about 5 wt%
- the amount of polyurethane in the protein polyurethane alloy can range from about 50 wt% to about 95 wt%, including subranges.
- the amount of polyurethane in the protein polyurethane alloy can range from about 50 wt% to about 95 wt%, about 55 wt% to about 95 wt%, about 60 wt% to about 95 wt%, about 65 wt% to about 95 wt%, about 70 wt% to about 95 wt%, about 75 wt% to about 95 wt%, about 80 wt% to about 95 wt%, about 85 wt% to about 95 wt%, about 90 wt% to about 95 wt%, about 50 wt% to about 90 wt%, about 50 wt% to about 85 wt%, about 50 wt% to about 80 wt%, about 50 wt% to about 75 wt%, about
- the weight percentages of protein and polyurethane in the protein polyurethane alloy can be any of the following.
- the amount of protein in the polyurethane alloy can range from about 5 wt% to about 50 wt% and the amount of polyurethane in the protein polyurethane alloy can range from about 50 wt% to about 95 wt%.
- the amount of protein in the polyurethane alloy can range from about 15 wt% to about 50 wt% and the amount of polyurethane in the protein polyurethane alloy can range from about 50 wt% to about 85 wt%.
- the amount of protein in the polyurethane alloy can range from about 20 wt% to about 50 wt% and the amount of polyurethane in the protein polyurethane alloy can range from about 50 wt% to about 80 wt%.
- the amount of protein in the polyurethane alloy can range from about 25 wt% to about 50 wt% and the amount of polyurethane in the protein polyurethane alloy can range from about 50 wt% to about 75 wt%.
- the amount of protein in the polyurethane alloy can range from about 30 wt% to about 50 wt% and the amount of polyurethane in the protein polyurethane alloy can range from about 50 wt% to about 70 wt%.
- the amount of protein in the polyurethane alloy can range from about 10 wt% to about 40 wt% and the amount of polyurethane in the protein polyurethane alloy can range from about 60 wt% to about 90 wt%.
- the amount of protein in the polyurethane alloy can range from about 15 wt% to about 40 wt% and the amount of polyurethane in the protein polyurethane alloy can range from about 60 wt% to about 85 wt%.
- the amount of protein in the polyurethane alloy can range from about 20 wt% to about 40 wt% and the amount of polyurethane in the protein polyurethane alloy can range from about 60 wt% to about 80 wt%.
- the amount of protein in the polyurethane alloy can range from about 20 wt% to about 35 wt% and the amount of polyurethane in the protein polyurethane alloy can range from about 65 wt% to about 80 wt%.
- the above-listed weight percent values and ranges can be based on the total weight of the protein polyurethane alloy. In some embodiments, the above-listed weight percent values and ranges can be based on the total weight of only protein and polyurethane in a protein polyurethane alloy. Unless otherwise specified, a weight percent value or range for the polyurethane and the protein is based on the total weight of only protein and polyurethane in a protein polyurethane alloy.
- the sum of the amount of protein plus the amount of polyurethane in the protein polyurethane alloy can be about 80 wt% or more.
- the sum of the amount of protein plus the amount of polyurethane in the protein polyurethane alloy can range from about 80 wt% to 100 wt%, about 82 wt% to 100 wt%, about 84 wt% to 100 wt%, about 86 wt% to 100 wt%, about 88 wt% to 100 wt%, about 90 wt% to 100 wt%, about 92 wt% to 100 wt%, about 94 wt% to 100 wt%, about 96 wt% to 100 wt%, or about 98 wt% to 100 wt%.
- the protein polyurethane alloy can include water making up a portion of the total weight percent of the material.
- the amount of water in the protein polyurethane alloy can range from about 1 wt% to about 10 wt%, including subranges.
- the amount of water in the protein polyurethane alloy can range from about 1 wt% to about 10 wt%, about 2 wt% to about 10 wt%, about 3 wt% to about 10 wt%, about 4 wt% to about 10 wt%, about 5 wt% to about 10 wt%, about 6 wt% to about 10 wt%, about 7 wt% to about 10 wt%, about 8 wt% to about 10 wt%, about 1 wt% to about 9 wt%, about 1 wt% to about 8 wt%, about 1 wt% to about 7 wt%, about 1 wt% to about 6 wt%, about 1 wt% to about 5 wt%, about 1 wt% to about 4 wt%, or about 1 wt% to about 3 wt%, or within a range having any two of these values as endpoints, inclusive of the endpoint
- the protein polyurethane alloy can be a protein polyurethane alloy as descried in U.S. Pub. No. 2021/0355326, which is hereby incorporated by reference in its entirety.
- Coated fibers according to embodiments described herein can comprise a core fiber and a coating disposed over the core fiber and comprising a protein dissolved within a polyurethane.
- FIG. 1 shows a coated fiber 100 according to some embodiments.
- Coated fiber 100 comprises a core fiber 110 and a coating 120 coated on core fiber 110.
- Coating 120 can comprise one or more protein polyurethane alloys as described herein.
- Coating 120 can be coated around all or a portion of core fiber 110. In other words, coating 120 can be coated around all or a portion of an outer surface 112 of core fiber 110. In some embodiments, coating 120 can be coated around the entirety of core fiber 110. In such embodiments, core fiber 110 can be surrounded by coating 120.
- coating 120 can be disposed over core fiber 110.
- coating 120 can be disposed over outer surface 112 of core fiber 110.
- coating 120 can be disposed on core fiber 110.
- coating 120 can be disposed on outer surface 112 of core fiber 110.
- Core fiber 110 can comprise one or more fiber materials.
- Suitable fiber materials for core fiber 110 include, but are not limited to natural fiber materials, for example cotton, linen, silk, wool, kenaf, flax, cashmere, angora, bamboo, bast, hemp, soya, seacell, milk or milk proteins, spider silk, chitosan, mycelium, cellulose including bacterial cellulose, or wood.
- Additional suitable fiber materials for core fiber 110 include, but are not limited to, synthetic fiber materials, for example polyesters, nylons, aromatic polyamides, or polyolefins such as polyethylene, polypropylene.
- core fiber 110 can comprise a cellulosic material like rayon, lyocell (for example, TENCELTM), modal, viscose, SORBTEK®, elastomers such as LYCRA®, spandex (for example, DORLASTAN®), or ELASTANE®, polyester-polyurethane copolymers, or aramids.
- core fiber 110 can comprise a polymeric fiber with functional particles in the polymer.
- Exemplary functional particles include ceramic particles mixed in a polymeric resin during an extrusion process for making the polymeric fibers. Such ceramic particles can provide the polymeric fibers with desirable heat dissipation and flame resistance properties.
- core fiber 110 can comprise fiber made of fruit pulp (e.g., grape pulp or apple pulp) or a pineapple fiber. In some embodiments, core fiber 110 can comprise fiber made from recycled materials, for example, recycled plastics. In some embodiments, core fiber 110 can comprise algae. In some embodiments, core fiber 110 can comprise cork.
- coated fiber 100 can comprise a coloring agent.
- the coloring agent can be a dye.
- Suitable dyes include, but are not limited to, a fiber reactive dye, an acid dye, a direct dye, or a natural dye.
- Exemplary dyes include but are not limited to, Azo structure acid dyes, metal complex structure acid dyes, anthraquinone structure acid dyes, and azo/diazo direct dyes.
- core fiber 110 can comprise the coloring agent.
- coating 120 can comprise the coloring agent.
- core fiber 110 and coating 120 can comprise the coloring agent.
- coated fiber 100 can have coating uptake of greater than or equal to 10%. “Coating uptake” defines the mass of coating 120 coated on core fiber 110 relative to the mass of core fiber 110. A coating uptake (U) is defined by Equation 1 below, where Mi is the mass of core fiber 110 before coating 120 is applied and M2 is the mass coated fiber 100. (Equation 1) [0105] In some embodiments, coated fiber 100 can have a coating uptake of greater than or equal to 15%. In some embodiments, coated fiber 100 can have a coating uptake of greater than or equal to 20%. In some embodiments, coated fiber 100 can have a coating uptake of greater than or equal to 25%. In some embodiments, coated fiber 100 can have a coating uptake of greater than or equal to 30%.
- coated fiber 100 can have a coating uptake of greater than or equal to 40%. In some embodiments, coated fiber 100 can have a coating uptake of greater than or equal to 50%. In some embodiments, coated fiber 100 can have a coating uptake of greater than or equal to 60%. In some embodiments, coated fiber 100 can have a coating uptake of greater than or equal to 70%. In some embodiments, coated fiber 100 can have a coating uptake of greater than or equal to 80%.
- coated fiber 100 can have a coating uptake ranging from about 10% to about 100%, including subranges.
- coated fiber 100 can have a coating uptake ranging from about 15% to about 100%, about 20% to about 100%, about 25% to about 100%, about 30% to about 100%, about 40% to about 100%, about 50% to about 100%, about 60% to about 100%, about 70% to about 100%, about 80% to about 100%, about 10% to about 90%, about 10% to about 80%, about 10% to about 70%, about 10% to about 60%, about 10% to about 50%, about 10% to about 40%, about 10% to about 30%, about 10% to about 25%, or about 10% to about 20%, or within a range having any two of these values as endpoints, inclusive of the endpoints.
- coated fiber 100 can have a coating uptake ranging from about 10% to about 110%.
- coating 120 can have a thickness 122, measured from outer surface 112 of core fiber to an outer surface of coating 120, of greater than or equal to about 100 nanometers. In some embodiments, thickness 122 can be greater than or equal to about 500 nanometers. In some embodiments, thickness 122 can be greater than or equal to about 1 micrometer (micron). In some embodiments, thickness 122 can be greater than or equal to about 10 microns.
- thickness 122 can range from about 100 nanometers to about 1 millimeter, including subranges. For example, thickness 122 can range from about 500 nanometers to about 1 millimeter, about 1 micron to about 1 millimeter, about 100 nanometers to about 10 microns, or about 100 nanometers to about 1 micron, or within a range having any two of these values as endpoints. [0109] In some embodiments, thickness 122 can be greater than or equal to 1% of an effective diameter 114 of core fiber 110. In some embodiments, thickness 122 can be greater than or equal to 2% of effective diameter 114 of core fiber 110. In some embodiments, thickness 122 can be greater than or equal to 5% of effective diameter 114 of core fiber 110.
- effective diameter 114 of core fiber 110 can be greater than or equal to about 0.01 millimeters. In some embodiments, effective diameter 114 of core fiber 110 can range from about 0.01 millimeters to about 10 millimeters.
- a portion of coating 120 can be integrated into core fiber 110.
- a first portion of coating 120 can be integrated into core fiber 110 and a second portion of coating 120 can define a coating layer on outer surface 112 of core fiber 110.
- the coating layer can have a thickness 122 as discussed above for coating 120.
- Core fiber 110 can have any suitable cross-sectional shape.
- the cross-sectional shape of core fiber 110 can be a square, a rectangle, a triangle, a circle, an ellipse, an oval, a pentagon, an octagon, or a star-shape.
- FIG. 2 illustrates core fiber 110 having a star-shaped cross section according to some embodiments.
- coating 120 can be a single continuous coating on core fiber 110. In such embodiments, coating 120 can be a single coating surrounding all or a portion of core fiber 110. In other embodiments, coating 120 can be a discontinuous coating comprising a plurality of discrete coating portions 124 disposed around core fiber 110. In such embodiments, coating 120 can comprise any suitable number of discrete coating portions 124, for example, two, three, four, five, six, seven, eight, or more coating portions.
- FIG. 3 illustrates a cross-section of a coated fiber comprising three discrete coating portions 124 on core fiber 110 according to some embodiments.
- FIG. 4 illustrates a cross-section of a coated fiber comprising six discrete coating portions 124 on core fiber 110 according to some embodiments.
- FIG. 5 illustrates a cross-section of a coated fiber comprising two discrete coating portions 124 on core fiber 110 according to some embodiments.
- coating 120 can be a partial coating surrounding only a portion of core fiber 110. In such embodiments, coating 120 does not surround the entirety of core fiber 110. For example, coating 120 can be partial coating surrounding about 50% of core fiber 110. As another example, coating 120 can be a partial coating surrounding about 75% of core fiber 110.
- FIG. 6 illustrates a cross-section of a coated fiber comprising a partial coating 120 according to some embodiments.
- FIG. 7 illustrates a cross-section of a coated fiber comprising a partial coating 120 according to some embodiments.
- one or more coated fibers 100 can be formed into a fabric or textile material using a technique such as weaving, knitting, spreading, felting, stitching, and/or crocheting.
- a first coated fiber 100 can be in contact with itself and/or a second coated fiber 100 at one or more points and can slide over itself and/or the second coated fiber 100 in at least one direction.
- one or more coated fibers 100 and one or more fibers not coated with a protein polyurethane alloy can be formed into a fabric or textile material using a technique such as weaving, knitting, spreading, felting, stitching, and/or crocheting.
- a coated fiber 100 can be in contact with itself and/or a fiber not coated with a protein polyurethane alloy at one or more points and can slide over itself and/or the fiber not coated with a protein polyurethane alloy in at least one direction.
- a plurality of coated fibers 100 can be formed into a nonwoven fabric or textile material.
- the coated fibers can be mechanically, chemically, or thermally bound to each other at some points and can still slide over each other in at least one direction at one or more positions within the material.
- one or more coated fibers 100 and one or more fibers not coated with a protein polyurethane alloy can be formed into a non-woven fabric or textile material.
- a coated fiber can be mechanically, chemically, or thermally bound to itself and/or a fiber not coated with a protein polyurethane alloy at some points and can still slide over itself and/or the fiber not coated with a protein polyurethane alloy in at least one direction at one or more positions within the material.
- the ability of one or more coated fibers and/or fibers not coated with a protein polyurethane alloy to slide relative to each other facilitates flexibility in a material.
- coating a surface of a fabric or textile material with a protein polyurethane alloy using, for example, a dipping process, a spraying process, or a roll-to-roll coating process can fix the fibers in a planar direction, which can prevent or inhibit the ability of the fibers to slide over one another. By fixing the fibers in a planar direction, haptic and/or drape properties can be affected.
- the amount of coating disposed on coated fibers within a fabric or textile material can be uniform through a cross-sectional thickness of the material.
- all the coated fibers within the fabric or textile material can have a coating uptake that is substantially the same.
- a coating uptake being “substantially the same” means that all the coated fibers within the fabric or textile material have an average coating uptake, the variation between the fiber with the highest coating uptake is no more than 10% higher than the average, and the variation between the fiber with the lowest coating uptake is no more than 10% lower than the average. For example, if all the coated fibers within the fabric or textile material have an average coating uptake of 50%, the fiber having the highest coating uptake can have a coating uptake of no higher than 55% and the fiber having the lowest coating uptake can have a coating uptake of no lower than 45%.
- Coated fiber 100 can be made by a method comprising coating core fiber 110 with coating 120 comprising a protein polyurethane alloy.
- the method of making coated fiber 100 can comprise applying a coating solution comprising the protein polyurethane alloy to core fiber 110 and drying the coated core fiber to form coated fiber 100.
- the method of making coated fiber 100 can comprise a dip coating process that comprises dipping core fiber 110 in the coating solution comprising the protein polyurethane alloy and drying the coated core fiber to form coated fiber 100.
- the method of making coated fiber 100 can comprise dying core fiber 110, coating 120, or both. In some embodiments, the method can comprise dying core fiber 110, coating 120, or both after coating 120 is coated on core fiber 110. In some embodiments, the method can comprise dying core fiber 110, coating 120, or both before coating 120 is coated on core fiber 110. In some embodiments, dying coating 120 before coating 120 is coated on core fiber 110 can comprise adding a dye to the coating solution comprising the protein polyurethane alloy.
- the coating solution comprising the protein polyurethane alloy can be formed by blending one or more proteins with one or more water-borne polyurethane dispersions in a liquid state. In some embodiments, the coating solution comprising the protein polyurethane alloy can be formed by blending one or more proteins dissolved or dispersed in an aqueous solution with one or more water-borne polyurethane dispersions in a liquid state. In some embodiments, the polyurethane dispersion can be ionic, and either anionic or cationic. In some embodiments, the polyurethane dispersion can be nonionic.
- one or more additives can be added to the coating solution.
- the additive(s) can influence the final properties of coating 120, coated fiber 100, or both.
- the additive(s) added can impact one or more of the following material properties of coating 120, coated fiber 100, or both: stiffness, elasticity, cohesive strength, tear strength, fire retardancy, chemical stability, or wet stability.
- Suitable additives include, but are not limited to, cross-linkers, fillers, dyes, pigments, plasticizers, waxes, rheological modifiers, flame retardants, antimicrobial agents, antifungal agents, antioxidants, UV stabilizers, mechanical foaming agents, chemical foaming agents, foam stabilizers, and the like.
- Suitable dyes include, but are not limited, to fiber reactive dyes or natural dyes.
- Suitable cross-linkers include, but are not limited to, epoxy -based crosslinkers, (for example, poly(ethylene glycol) diglycidyl ether (PEGDE) available from Sigma Aldridge), isocyanate-based cross-linkers (for example, X-Tan® available from Lanxess), and carbodiimide-based cross-linkers.
- Suitable foaming agents include, HeiQ Chemtex 2216-T (a stabilized blend of nonionic and anionic surfactants), HeiQ Chemtex 2241 -A (a modified HEUR (hydrophobically-modified ethylene oxide urethane) thickener), HeiQ Chemtex 2243 (a non-ionic silicone dispersion), or HeiQ Chemtex 2317 (a stabilized blend of nonionic and anionic surfactants) foam stabilizers available from HeiQ Chemtex.
- Suitable antimicrobial/antifungal agents include Ultra-Fresh DW-56, or other antimicrobial/antifungal agents used in the leather industry.
- Suitable flame retardants include Cetaflam® DB9 (organophosphorous compounds containing C-PO(OH)2 or C-PO(OR)2 groups with the carbon chain containing polymers), Cetaflam® PD3300 (organophosphorous compounds containing C ⁇ PO(OH)2 or C-PO(OR)2 groups with the carbon chain containing polymers), or other flame retardants used for coated textiles.
- Suitable fillers include, but are not limited to, thermoplastic microspheres, for example, Expancel® Microspheres.
- Suitable rheological modifiers include, but are not limited to, alkali swellable rheological modifiers, hydrophobically- modified ethylene oxide-based urethane (HEUR) rheological modifiers, and volume exclusion thickeners.
- Exemplary alkali swellable rheological modifiers include but are not limited to, AcrysolTM DR-106, AcrysolTM ASE-60 from Dow Chemicals, Texicryl® 13-3131, and Texicryl® 13-308 from Scott-Bader.
- Exemplary HEUR modifiers include, but are not limited to, RM-4410 from Stahl and Chemtex 2241 -A from HeiQ.
- Exemplary volume exclusion thickeners include, but are not limited to, WalocelTM XM 20000 PV from Dow Chemicals and Methyl-Hydroxyethyl Cellulose from Sigma- Aldrich.
- a fabric or textile material can be made by coating one or more core fibers with a coating comprising a protein dissolved within a polyurethane to form one or more coated fibers 100, and after forming the one or more coated fibers 100, mechanically entangling the one or more coated fibers 100 to form the fabric or textile material.
- exemplary mechanical entangling techniques include, but are not limited to, weaving, knitting, spreading, felting, stitching, crocheting, or any other similar technique for making a fabric or textile material.
- a soy protein isolate (SPI) solution was prepared by dissolving 3.75 g of SPI (SUPRO® XT 221D-IP; DuPont; available from Solae LLC) in 21.25 mL of a 0.05 mol/L NaOH (sodium hydroxide) aqueous solution in a 50 mL glass beaker. The solution was heated to 50 °C and stirred at 600 rotations per minute (rpm) with an overhead mixer for 30 minutes to dissolve the SPI. The solids content of the solution after mixing was 15 wt% soy protein solids.
- SPI soy protein isolate
- a soy protein polyurethane alloy solution was prepared by adding 2.5 g of the SPI solution to 20 g of L3360 from Hauthaway in a 100 mL beaker. The solution was then mixed with an overhead mixer at 150 rpm for 5 minutes. The solution appeared homogenous after mixing. The dry ratio of L3360 solids to SPI solids was 95 to 5 (i.e., about 5 wt% SPI).
- each coated fiber sample was measured and the average coating uptake for each respective fiber type was measured by normalizing the dry weight changes of the individual fibers before and after coating and dividing by the original dry weight of the uncoated fiber.
- Table 2 shows the average coating uptake for each of the five fiber types.
- the average coating uptake is the average coating uptake for the five samples of each respective fiber type.
- the maximum tensile strength and tensile strain (i.e., the percent elongation at break) for samples of the uncoated and coated fibers were also measured using a tensile test method based on ASTM D2256/D2256M with a modified gauge length of 20 mm and testing speed of 100 mm/min. No significant changes in tensile strength or tensile strain were observed between the uncoated and coated fibers.
- a sample of each of the five coated fibers from Example 1 was dyed with Acid Red 362 dye from Panchmahal Dyestuff Industries using the following process. 500 mg of the dye was added to 150 mL of DI water. The pH of the dye solution was measured and a IN HC1 (hydrochloric acid) solution was added to the dye solution until the pH was between 3 and 4. After a pH of 3 to 4 was achieved, the dye solution was heated to 50 °C on a hot plate. Then each of the five coated fiber samples was placed in the heated dye solution for 20 minutes. After dying for 20 minutes, each fiber was removed from the dye solution and rinsed with warm water. [0132] Uncoated samples of each of the five fibers were also dyed using the same dye and process. Based on a visual inspection, the coated DORLASTAN® spandex yam exhibited significantly more dye color uptake compared to the uncoated and dyed DORLASTAN® spandex fiber.
- a soy protein polyurethane alloy solution was prepared by adding 5.2 g of the SPI solution from Example 1 to 20 g of L3360 from Hauthaway in a 100 mL beaker. The solution was then mixed with an overhead mixer at 150 rpm for 5 minutes. The solution appeared homogenous after mixing. The dry ratio of L3360 solids to SPI solids was 90 to 10 (i.e., about 10 wt% SPI).
- Red 362 dye from Panchmahal Dyestuff Industries using the same process as described in Example 2. Based on a visual inspection, the coated DORLASTAN® spandex yarn, the coated Robison-Anton polyester yarn, and the coated Shuford TENCELTM yam exhibited significantly more dye color uptake compared to the uncoated and dyed samples of the same fibers.
- a dyed soy protein isolate (SPI) solution was prepared by dissolving 3.75 g SPI (SUPRO® XT 221D-IP; DuPont; available from Solae LLC) in 21.25 mL of a 0.1 mol/L NaOH aqueous solution in a 50 mL glass beaker. 16 mg of Blue-21 reactive dye from Khushi Dye Chem was then added to the 25 g solution. The solution was then heated to 50 °C and stirred at 600 rpm with an overhead mixer for 30 minutes to dissolve the SPI. The solids content of the dyed solution after mixing was about 15 wt% soy protein solids with dye.
- a dyed soy protein polyurethane alloy solution was prepared by adding 2.5 g of the dyed SPI solution to 20 g of L3360 from Hauthaway in a 100 mL beaker. The solution was then mixed with an overhead mixer at 150 rpm for 5 minutes. The solution appeared homogenous after mixing. The dry ratio of L3360 solids to SPI solids was 95 to 5.
- a dyed soy protein polyurethane alloy solution was prepared by adding 5.2 g of the dyed SPI solution from Example 5 to 20 g of L3360 from Hauthaway in a 100 mL beaker. The solution was then mixed with an overhead mixer at 150 rpm for 5 minutes. The solution appeared homogenous after mixing. The dry ratio of L3360 solids to SPI solids was 90 to 10.
- the coated yams appeared uniformly and evenly dyed. Based on a visual inspection, the coated and dyed yarns exhibited a significant color change compared to uncoated and undyed DORLASTAN® spandex yam.
- a sample of each of the five coated fibers from Examples 1 and 3 is dyed with Blue-21 reactive dye from Khushi Dye Chem using the following process. 500 mg of the dye is added to 150 mL of DI water. The pH of the dye solution is measured and a IN NaOH solution is added to the dye solution until the pH is between 8 and 9. After a pH of 8 to 9 is achieved, the dye solution is heated to 50 °C on a hot plate. Then each of the five coated fiber samples is placed in the heated dye solution for 20 minutes. After dying for 20 minutes, each fiber is removed from the dye solution and rinsed with warm water.
- a cellulase solution is prepared by dissolving 4.17 g of cellulase (Native Trichoderma sp. Cellulase; Creative Enzymes®) in 20.85 mL of DI water in a 50 mL glass beaker. The solution is stirred at about 600 rpm with an overhead mixer for 30 minutes to dissolve the cellulase.
- a cellulase polyurethane alloy solution is prepared by adding 2.2 g of the cellulase solution to 20 g of L3360 from Hauthaway in a 100 mL beaker. The solution is then mixed with an overhead mixer at about 150 rpm for 5 minutes.
- the following five different types of fibers are coated with the cellulase polyurethane alloy solution: (1) DORLASTAN® spandex yarn, (2) Robison-Anton polyester yarn, (3) Robison-Anton nylon yarn, (4) TENCELTM yam from Shuford Yarns LLC, and (5) silk thread from Clover Needlecraft, Inc.
- the five fiber types are coated with the cellulase polyurethane alloy solution using the following process. First, the fiber is dipped into the solution and the solution and fiber are lightly stirred for 10 seconds. After stirring, the fiber is removed from the solution and excess solution on the fiber is removed by sliding the fiber against a solid edge to obtain a substantially even coating. Then the coated fiber is dried in an oven at 75 °C for 10 minutes and cured in a separate oven at 120 °C for additional 10 minutes.
- a soy protein isolate (SPI) solution was prepared as described in Example 1.
- Four coated yarn sample types (Sample Types 9A - 9D) were prepared by coating the yam types listed below in Table 4 with two soy protein polyurethane alloy solutions — a higher viscosity solution with a rheology modifier and a lower viscosity solution without the rheology modifier.
- Both of the two soy protein polyurethane alloy solutions were prepared by adding 205.88 g of the SPI solution to 794.12 g of L3360 from Hauthaway in a 1000 mL beaker. Each solution was then mixed with an overhead mixer at 150 rpm for 5 minutes.
- a rheology modifier (RM-4410, from Stahl) was added at 2 wt% of the total solution (20 grams) and a green pigment (PP-39-61 from Permutex) was added at 1 wt% of the total solution.
- a green pigment PP-39-61 from Permutex
- PP-39-114 from Stahl CAMOTEX® was added at 1 wt% of the total solution.
- each solution was mixed with an overhead mixer at 300 rpm for 5 minutes. Both solutions appeared homogenous after mixing. The dry ratio of L3360 solids to SPI solids in both solutions was 90 to 10.
- the maximum tensile strength and tensile strain (i.e., the percent elongation at break) for three yams of Sample Type C and three uncoated Shuford TENCELTM yarns were measured using a tensile test method based on ASTM D2256/D2256M with a modified gauge length of 20 mm and testing speed of 100 mm/min. The maximum tensile strength and tensile strain were slightly lower for the coated yarns of Sample Type C.
- a soy protein isolate (SPI) solution was made by dissolving 3.75 g 221D-IP soy protein isolate (SUPRO XT 221D-IP; DuPont; available from Solae LLC) into 21.25 mL of a 0.05 mol/L NaOH aqueous solution in a 50 mL glass beaker. The solution was heated to 50 °C and stirred at 600 rpm with an overhead mixer for 30 minutes. The solids content of the final soy protein solution was 15% soy protein solids.
- SPI soy protein isolate
- a soy protein polyurethane alloy solution was prepared by adding 5.2 g of the SPI solution to 20 g of L3360 from Hauthaway in a 100 mL beaker. The solution was then mixed with an overhead mixer at 150 rpm for 5 minutes. The solution appeared homogenous after mixing. The dry ratio of L3360 solids to SPI solids was 90 to 10 (i.e., about 10 wt% SPI).
- a first cellulase polyurethane alloy solution was prepared by adding 2.43 g of cellulase (Native Trichoderma sp. Cellulase; Creative Enzymes) to 27.82 g of L3360 from Hauthaway in a 40 mL beaker. The solution was mixed at room temperature with an overhead mixer at 500 rpm for 30 minutes. The solution appeared homogenous after mixing. The dry ratio of L3360 solids to cellulase protein solids was 90 to 10 (i.e., about 10 wt% cellulase).
- a second cellulase polyurethane alloy solution was prepared using the same method as the first cellulase polyurethane alloy solution, except 1.51 g of a carbodiimide crosslinker solution (XR-5577 available from Stahl) was added to the 40 mL beaker. The second cellulase polyurethane alloy solution also appeared homogenous after mixing.
- a carbodiimide crosslinker solution XR-5577 available from Stahl
- a bovine serum albumin solution was made by dissolving 1.20 g of bovine serum albumin into 10.08 g of water in a 25 mL glass beaker. The solution was then heated to 50 °C and stirred at 600 rpm with an overhead mixer for 30 minutes. The solids content of the final bovine serum albumin solution was 10 wt% protein solids.
- a bovine serum albumin polyurethane alloy solution was prepared by adding the bovine serum albumin solution to 28.8 g of L3360 from Hauthaway in a 50 mL beaker. The solution was then mixed with an overhead mixer at 150 rpm for 5 minutes at room temperature. The solution appeared homogenous after mixing. The dry ratio of L3360 solids to protein solids was 90 to 10 (i.e., about 10 wt% bovine serum albumin).
- a gelatin protein solution was made by dissolving 1.20 g of gelatin from porcine skin into 10.08 g of water in a 25 mL glass beaker. The solution was then heated to 50 °C and stirred at 600 rpm with an overhead mixer for 30 minutes. The solids content of the final gelatin protein solution was 10 wt% gelatin protein solids.
- a gelatin protein polyurethane alloy solution was prepared by adding the gelatin protein solution to 28.8 g of L3360 from Hauthaway in a 50 mL beaker. The solution was then mixed with an overhead mixer at 150 rpm for 5 minutes at room temperature. The solution appeared homogenous after mixing. The dry ratio of L3360 solids to protein solids was 90 to 10 (i.e., about 10 wt% gelatin).
- Alloy Solutions 11 A - 1 IF Six protein polyurethane alloy solutions (Alloy Solutions 11 A - 1 IF) were made according to the following process. First, a soy protein isolate (SPI) solution was made as described in Example 10. Then, Alloy Solutions 11 A - 1 IF were prepared by mixing the amount (in grams) of the SPI solution, the amount (in grams) of polyurethane dispersion, the additive as shown in Table 6 to respective 100 mL beakers. The alloy solution in each respective beaker was heated to 50 °C and mixed with an overhead mixer at 150 rpm for 5 minutes. All the Alloy Solutions 11 A - 1 IF appeared homogenous after mixing.
- SPI soy protein isolate
- Hydran WLS-286BP in Table 6 is an alphatic / polycarbonate type polyurethane dispersion available from DIC Gobal.
- Impranil DLN W50 in Table 6 is an anionic aliphatic polyester-polyurethane dispersion available from Covestro.
- SE 2140 waterbased PUD in Table 6 is an aliphatic polyurethane dispersion.
- L3360 in Table 6 is L3360 from Hauthaway.
- Stahl RM-4410 is Table 6 is RM-4410 rheology modifier from Stahl.
- each yam was weighed and the coating uptake was measured by normalizing the dry weight changes of the individual yarns before and after coating and dividing by the original dry weight of the uncoated yam.
- the coating uptake for each yarn is shown below in Table 7.
- each yarn was tested for yam-on-yam abrasion resistance according to ASTM D6611-16 (“Standard Test Method for Wet and Dry Yarn-on-Yam Abrasion Resistance”) with a weight of 50 g and 3 twists in the inter wrapped yarn region.
- the abrasion resistance measured for each yam is also shown in Table 7.
- Uncoated Shuford TENCELTM yarns were also tested for abrasion resistance. The abrasion resistance for the uncoated Shuford TENCELTM yarns was between 25 and 100 cycles.
- a first dyed cellulase polyurethane alloy solution was prepared using the following method. First, 2.43 g of cellulase (Native Trichoderma sp. Cellulase; Creative Enzymes) was mixed with 27.82 g of L3360 in a 40 mL beaker. 3 mg of Blue-21 reactive dye available from Chem International. Inc. (Blue-21 dye) was then added to the solution and the solution was mixed with an overhead mixer at 500 rpm for 30 minutes at room temperature. 10 pL of 10N NaOH was slowly added into the solution while mixing. The solution appeared homogenous after mixing.
- a second dyed cellulase polyurethane alloy solution was prepared using the same method as the first cellulase polyurethane alloy solution, except 1.51 g of a carbodiimide crosslinker solution (XR-5577 available from Stahl) was added to the 40 mL beaker.
- the second cellulase polyurethane alloy solution also appeared homogenous after mixing.
- a dyed bovine serum albumin polyurethane solution was made using the following process. First, 1.20 g of bovine serum albumin was added into 10.08 g of water in a 25 mL glass beaker. Then, 3 mg of Blue-21 dye was added to the solution and the solution was heated to 50 °C and stirred at 600 rpm with an overhead mixer for 30 minutes. Then, the dyed bovine serum albumin solution was added to 28.8 g of L3360 from Hauthaway in a 50 mL beaker. The solution was then mixed with an overhead mixer at 150 rpm for 5 minutes at room temperature. The solution appeared homogenous after mixing. The dry ratio of L3360 solids to protein solids was 90 to 10 (i.e., about 10 wt% bovine serum albumin).
- a dyed gelatin polyurethane solution was made using the following process. First, 1.20 g of gelatin from porcine skin was added into 10.08 g of water in a 25 mL glass beaker. Then, 3 mg of the Blue-21 dye was added to the solution and the solution was heated to 50 °C and stirred at 600 rpm with an overhead mixer for 30 minutes. Then, the dyed gelatin protein solution was added to 28.8 g of L3360 from Hauthaway in a 50 mL beaker. The solution was then mixed with an overhead mixer at 150 rpm for 5 minutes at room temperature. The solution appeared homogenous after mixing. The dry ratio of L3360 solids to protein solids was 90 to 10 (i.e., about 10 wt% gelatin)
- the five different yarn types were then coated with each respective dyed polyurethane alloy solution.
- the five different yam types were: (i) DORLASTAN® Spandex yarn, (ii) Robison-Anton polyester yarn, (iii) Robison-Anton nylon yam, (iv) Shuford TENCELTM yarn, and (v) silk thread from Clover Needlecraft, Inc.
- Each yam was coated in each respective solution using the following process. Each yam was dipped into the respective alloy solution and stirred for 10 minutes. After stirring, each yam was taken out of the alloy solution and excess coating solution was removed by sliding the yam against a solid edge. After removing excess coating, each yarn was dried in an oven at 75 °C for 10 minutes, and then cured in a separate oven at 120 °C for additional 10 minutes.
- each yarn coated with each respective dyed polyurethane alloy solution appeared uniformly and evenly dyed.
- Coated yam types from Examples 10 and 11 were dyed with the dyes as shown below in Table 8.
- Acid Blue 158 in Table 8 is Acid Blue 158 dye from Panchmahal Dyestuff Industries.
- Reactive Black 5 in Table 8 is Reactive Black 5 dye from Dye-Chem International.
- Acid Red 362 in Table 8 is Acid Red 362 dye from Panchmahal Dyestuff Industries.
- Reactive Blue 11 in Table 8 is Reactive Blue 11 dye from Dye-Chem International.
- Reactive Blue 21 in Table 8 is Reactive Blue 21 dye from Dye-Chem International.
- Coated yams dyed with Acid Blue 158 were dyed according to the following process. 650 mg of Acid Blue 158 dye was added to 200 mL of DI water in a beaker. The pH of the solution was measured and drops of IN HC1 were added to the solution until the pH read between 3 and 4. The beaker with the solution was then placed on a hot plate and heated to 60 °C. Then the yarns were placed in the heated solution and allowed to soak for 1 hour. After soaking, the yarns were removed from the beaker and washed with warm water. Uncoated yams were also dyed using the same process.
- Coated yams dyed with Reactive Black 5 were dyed according to the following process. 650 mg of Reactive Black 5 dye was added to 200 mL of DI water in a beaker. The pH of the solution was measured and drops of IN NaOH were added to the solution until the pH read between 9 and 10. The beaker with the solution was then placed on a hot plate and heated to 60 °C. Then the yarns were placed in the heated solution and allowed to soak for 1 hour. After soaking, the yarns were removed from the beaker and washed with warm water. Uncoated yarns were also dyed using the same process.
- Coated yams dyed with Acid Red 362 were dyed according to the following process. 500 mg of Acid Red 362 dye was added to 150 mL of DI water in a beaker. The pH of the solution was measured and drops of IN HC1 were added to the solution until the pH read between 3 and 4. The beaker with the solution was then placed on a hot plate and heated to 60 °C for Yam Types 10F and 10H, and 50 °C for Yarn Types 10P, 10R, 10T and 10U, TENCELTM yarn coated with Solution 1 IE, and TENCELTM yarn coated with Solution 1 IF. The yams were placed in the heated solution and allowed to soak.
- Yarn Types 10F and 10H were allowed to soak for 16 hours, while Yarn Types 10P, 10R, 10T and 10U, TENCELTM yarn coated with Solution 1 IE, and TENCELTM yarn coated with Solution 1 IF were allowed to soak for 30 minutes. After soaking, the yams were removed from the beaker and washed with warm water. Uncoated yams were also dyed using the same processes.
- Coated yams dyed with Reactive Blue 11 were dyed according to the following process. 650 mg of Reactive Blue 11 dye was added to 200 mL of DI water in a beaker. The pH of the solution was measured and drops of IN NaOH were added to the solution until the pH read between 9 and 10. The beaker with the solution was then placed on a hot plate and heated to 60 °C. Then the yarns were placed in the heated solution and allowed to soak for 16 hours. After soaking, the yams were removed from the beaker and washed with warm water. Uncoated yarns were also dyed using the same process.
- Coated yams dyed with Reactive Blue 21 were dyed according to the following process. 650 mg of Reactive Blue 21 dye was added to 200 mL of DI water in a beaker. The pH of the solution was measured and drops of IN NaOH were added to the solution until the pH read between 9 and 10. The beaker with the solution was then placed on a hot plate and heated to 50 °C. Then the yarns were placed in the heated solution and allowed to soak for 1 hour. After soaking, the yarns were removed from the beaker and washed with warm water. Uncoated yarns were also dyed using the same process.
- SEQ ID NO: 1 Collagen Fragment
Abstract
Coated fibers including a core fiber and a coating disposed over the core fiber. The coating can include a protein dissolved within a polyurethane. The coating can be dyed using, for example, an acid dye or a reactive dye. The coated fibers can be made by applying a coating solution including the protein dissolved within the polyurethane to the core fiber.
Description
COATED FIBERS COMPRISING A PROTEIN POLYURETHANE ALLOY AND METHODS OF MAKING THE SAME
REFERENCE TO SEQUENCE LISTING SUBMITTED ELECTRONICALLY
[0001] The content of the electronically submitted sequence listing in XML file (Name: 4431_087PC02_Seqlisting_ST26.xml; Size: 2,683 Bytes; and Date of Creation: December 13, 2022) filed with the application is incorporated herein by reference in its entirety.
FIELD
[0002] This disclosure relates to fibers coated with a coating comprising a protein polyurethane alloy, the protein polyurethane alloy comprising one or more proteins dissolved in a polyurethane. In some embodiments, the fibers can be used to make a textile or fabric article, for example, a textile or fabric article previously prepared from natural leather.
BACKGROUND
[0003] Leather is a versatile product used across many industries, including the furniture industry, where leather is regularly used as upholstery, the clothing industry, where leather is used to manufacture pants and jackets, the shoe industry, where leather is used to prepare casual and dress shoes, the luggage industry, the handbag and accessory industry, and in the automotive industry. The global trade value for leather is high, and there is a continuing and increasing demand for leather products. However, there are variety of costs, constraints, and social concerns associated with producing natural leather. Foremost, natural leathers are produced from animal skins, and as such, requires raising and slaughtering livestock. Raising livestock requires enormous amounts of feed, pastureland, water, and fossil fuels and contributes to air and waterway pollution, through, for example, greenhouse gases like methane. Leather production also raises social concerns related to the treatment of animals. In recent years, there has also been a fairly well documented decrease in the availability of traditional high quality hides. For at least these reasons, alternative means to meet the demand for leather are desirable.
[0004] Further, other fabric materials, such as cotton and spandex, are used across many industries, including the furniture industry and the clothing industry. The demand for such fabric materials is high and there is a continuing need for improved fabric materials.
BRIEF SUMMARY
[0005] The present disclosure provides fibers coated with a protein polyurethane alloy and suitable for use in a variety of applications, including textile and fabric applications.
[0006] A first embodiment (1) of the present disclosure is directed to a coated fiber comprising a core fiber and a coating disposed over the core fiber, the coating comprising a protein dissolved within a polyurethane.
[0007] In a second embodiment (2), the protein of the first embodiment (1) is a soy protein.
[0008] In a third embodiment (3), the soy protein of the second embodiment (2) is soy protein isolate.
[0009] In a fourth embodiment (4), the coated fiber of any one of embodiments (1) - (3) further comprises a dye.
[0010] In a fifth embodiment (5), the coating of the coated fiber of the fourth embodiment (4) comprises the dye.
[0011] In a sixth embodiment (6), the coated fiber of any one of embodiments (1) - (5) has a coating uptake of greater than or equal to about 10%.
[0012] In a seventh embodiment (7), the coated fiber of any one of embodiments (1) - (5) has a coating uptake ranging from about 10% to about 100%.
[0013] In an eighth embodiment (8), the coating of any one of embodiments (1) - (7) has a thickness of greater than or equal to about 100 nanometers.
[0014] In a ninth embodiment (9), the coating of any one of embodiments (1) - (7) has a thickness ranging from about 100 nanometers to about 1 millimeter.
[0015] In a tenth embodiment (10), the coating of any one of embodiments (1) - (9) has a thickness greater than or equal to 1% of an effective diameter of the core fiber.
[0016] In an eleventh embodiment (11), the coating of any one of embodiments (1) - (10) comprises about 5 wt% to about 50 wt% of the protein and about 50 wt% to about 95 wt% of the polyurethane.
[0017] In a twelfth embodiment (12), the protein of any one of embodiments (1) or (4) - (11) is an enzyme.
[0018] In a thirteenth embodiment (13), the protein of any one of embodiments (1) or (4) - (11) is selected from the group consisting of: soy protein, collagen, gelatin, bovine serum albumin, pea protein, egg white albumin, casein protein, peanut protein, edestin protein, whey protein, karanja protein, hemp protein, an enzyme, and cellulase.
[0019] A fourteenth embodiment (14) is directed to a method of making a coated fiber, the method comprising coating a core fiber with a coating comprising a protein dissolved within a polyurethane.
[0020] In a fifteenth embodiment (15), coating the core fiber according to the fourteenth embodiment (14) comprises a dip coating process.
[0021] In a sixteenth embodiment (16), the method of the fourteenth embodiment (14) or the fifteenth embodiment (15) further comprises dying the coating.
[0022] In a seventeenth embodiment (17), the coating of the sixteenth embodiment (16) is dyed after the coating is coated on the core fiber.
[0023] In an eighteenth embodiment (18), the coating of the sixteenth embodiment (16) is dyed before the coating is coated on the core fiber.
[0024] A nineteenth embodiment (19) is directed to a material comprising a plurality of the coated fibers according to any one of embodiments (1) - (13), wherein a first coated fiber is in contact with a second coated fiber, and wherein the first and second coated fibers can slide over each other.
[0025] In a twentieth embodiment (20), the material of the nineteenth embodiment (19) further comprises a fiber not coated with a protein dissolved within a polyurethane, wherein the first coated fiber is in contact with the fiber not coated with a protein dissolved within a polyurethane, and wherein the first coated fiber and the fiber not coated with a protein dissolved within a polyurethane can slide over each other.
[0026] In a twenty-first embodiment (21), the amount of the coating disposed on the coated fibers within the material of the nineteenth embodiment (19) is uniform through a cross-sectional thickness of the material such that all the coated fibers within the material have a coating uptake that is substantially the same.
BRIEF DESCRIPTION OF THE FIGURE
[0027] The accompanying figure, which is incorporated herein, forms part of the specification and illustrates embodiments of the present disclosure. Together with the description, the figure further serves to explain the principles of and to enable a person skilled in the relevant art(s) to make and use the disclosed embodiments. The figure is intended to be illustrative, not limiting. Although the disclosure is generally described in the context of these embodiments, it should be understood that it is not intended to limit the scope of the disclosure to these particular embodiments.
[0028] FIG. 1 illustrates a coated fiber according to some embodiments.
[0029] FIG. 2 illustrates a coated fiber having a star-shaped core fiber according to some embodiments.
[0030] FIGs. 3-5 illustrate coated fibers including discontinuous coatings according to some embodiments.
[0031] FIGs. 6 and 7 illustrate partially coated fibers according to some embodiments.
DETAILED DESCRIPTION
[0032] The indefinite articles “a,” “an,” and “the” include plural referents unless clearly contradicted or the context clearly dictates otherwise.
[0033] The term “comprising” is an open-ended transitional phrase. A list of elements following the transitional phrase “comprising” is a non-exclusive list, such that elements in addition to those specifically recited in the list can also be present. The phrase “consisting essentially of’ limits the composition of a component to the specified materials and those that do not materially affect the basic and novel characteristic(s) of the component. The phrase “consisting of’ limits the composition of a component to the specified materials and excludes any material not specified.
[0034] Where a range of numerical values comprising upper and lower values is recited herein, unless otherwise stated in specific circumstances, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the disclosure or claims be limited to the specific values recited when defining a range. Further, when an amount, concentration, or other value or parameter is given as a range, one or more ranges, or as list of upper values and lower values, this is to be
understood as specifically disclosing all ranges formed from any pair of any upper range limit or value and any lower range limit or value, regardless of whether such pairs are separately disclosed. Finally, when the term “about” is used in describing a value or an end-point of a range, the disclosure should be understood to include the specific value or end-point referred to. Whether or not a numerical value or end-point of a range recites “about,” the numerical value or end-point of a range is intended to include two embodiments: one modified by “about,” and one not modified by “about.”
[0035] As used herein, the term “about” refers to a value that is within ± 10% of the value stated. For example, about 3 MPa can include any number ranging from 2.7 MPa to 3.3 MPa.
[0036] As used herein, the phrase “disposed on” means that a first component (e.g., a coating) is in direct contact with a second component. A first component “disposed on” a second component can be deposited, formed, placed, or otherwise applied directly onto the second component. In other words, if a first component is disposed on a second component, there are no components between the first component and the second component.
[0037] As used herein, the phrase “disposed over” means other components (e.g., layers or substrates) may or may not be present between a first component and a second component.
[0038] As used herein, a “bio-based polyurethane” is a polyurethane where the building blocks of polyols, such as diols and diacids like succinic acid, are derived from a biological material such as corn starch.
[0039] As used herein, the term “substantially free of’ means that a component is present in a detectable amount not exceeding about 0.1 wt%.
[0040] As used herein, the term “free of’ means that a component is not present in a blend or material (e.g., a protein polyurethane alloy), even in trace amounts.
[0041] As used herein, a “fiber” refers to a construct having a length that is substantially larger than its effective diameter. A “fiber” may be a filament, a thread, a yarn (for example, a knitted or woven yam), a cable, a cord, a fiber tow, a tape, a ribbon, a monofilament, a braid, a string, or any other form of material that can be spooled. In some embodiments, a fiber can have a length that is at least two times larger than its effective diameter. In some embodiments, a fiber can have a length that is at least ten times larger than its effective diameter. In some embodiments, a fiber can have a length that is at least
100 times larger than its effective diameter. In some embodiments, a fiber can have a length that is at least 200 times larger than its effective diameter. In some embodiments, a fiber can have a length that is at least 300 times larger than its effective diameter. In some embodiments, a fiber can have a length that is at least 500 times larger than its effective diameter.
[0042] An “effective diameter” is used herein to describe the diameter of a fiber, but this term should not be interpreted as requiring a fiber to have a circular diameter or shape. Instead, a fiber can have a non-circular shape, and in such embodiments, the term “effective diameter” is intended to refer to the maximum cross-sectional dimension of the shape. For example, the “effective diameter” of a fiber having an elliptical cross-sectional shape would be the length of the major axis of the elliptical shape. For a fiber having an effective diameter that varies along the length of the fiber, the effective diameter is the largest effective diameter.
[0043] As used herein “collagen” refers to the family of at least 28 distinct naturally occurring collagen types including, but not limited to collagen types I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, and XX. The term collagen as used herein also refers to collagen prepared using recombinant techniques. The term collagen includes collagen, collagen fragments, collagen-like proteins, triple helical collagen, alpha chains, monomers, gelatin, trimers and combinations thereof. Recombinant expression of collagen and collagen-like proteins is known in the art (see, e.g., Bell, EP 1232182B1, Bovine collagen and method for producing recombinant gelatin; Olsen, et al., U.S. Patent No. 6,428,978 and VanHeerde, et al., U.S. Patent No. 8,188,230, incorporated by reference herein in their entireties) Unless otherwise specified, collagen of any type, whether naturally occurring or prepared using recombinant techniques, can be used in any of the embodiments described herein. That said, in some embodiments, the collagen described herein can be prepared using bovine Type I collagen. Collagens are characterized by a repeating triplet of amino acids, -(Gly-X-Y)n-, so that approximately one-third of the amino acid residues in collagen are glycine. X is often proline and Y is often hydroxyproline. Thus, the structure of collagen may consist of three intertwined peptide chains of differing lengths. Different animals may produce different amino acid compositions of the collagen, which may result in different properties (and differences in the resulting leather).
[0044] Any type of collagen, truncated collagen, unmodified or post-translationally modified, or amino acid sequence-modified collagen can be used as part of the protein polyurethane alloy.
[0045] In some embodiments, the collagen can be plant-based collagen. For example, the collagen can be a plant-based collagen made by CollPlant.
[0046] In some embodiments, a collagen solution can be fibrillated into collagen fibrils. As used herein, collagen fibrils refer to nanofibers composed of tropocollagen or tropocollagen-like structures (which have a triple helical structure). In some embodiments, triple helical collagen can be fibrillated to form nanofibrils of collagen.
[0047] In some embodiments, a recombinant collagen can comprise a collagen fragment of the amino acid sequence of a native collagen molecule capable of forming tropocollagen (trimeric collagen). A recombinant collagen can also comprise a modified collagen or truncated collagen having an amino acid sequence at least 70, 80, 90, 95, 96, 97, 98, or 99% identical or similar to a native collagen amino acid sequence (or to a fibril forming region thereof or to a segment substantially comprising [Gly-X-Y]n). In some embodiments, the collagen fragment can be a 50 kDa portion of a native collagen. Native collagen sequences include the amino acid sequences of CollAl, CollA2, and Col3 Al, described by Accession Nos. NP_001029211.1, NP_776945.1 and NP_001070299.1, which are incorporated by reference. In some embodiments, the collagen fragment can be a portion of human collagen alpha-l(III) (Col3Al; Uniprot # P02461, Entrez Gene ID # 1281). In some embodiments, the collagen fragment can comprise the amino acid sequence listed as SEQ ID NO: 1.
[0048] Methods of producing recombinant collagen and recombinant collagen fragments are known in the art. For example, U.S. Pub. Nos. 2019/0002893, 2019/0040400, 2019/0093116, and 2019/0092838 provide methods for producing collagen and collagen fragments that can be used to produce the recombinant collagen and recombinant collagen fragments disclosed herein. The contents of these four publications are incorporated by reference in their entirety.
[0049] Coated fibers described herein comprise a core fiber coated with a coating comprising a protein polyurethane alloy. The protein polyurethane alloys described herein comprise a protein dissolved within a polyurethane, or a plurality of polyurethanes. In particular embodiments, the protein polyurethane alloys described herein can comprise a protein that is miscible with only one of a plurality of phases of the polyurethane, or the
plurality of polyurethanes, with which it is blended. For example, in some embodiments, the protein polyurethane alloy can include a protein that is miscible with only the hard phase of the polyurethane, or the plurality of polyurethanes, having both a hard phase and a soft phase. Protein polyurethane alloys described herein can be free of or substantially free of protein in form of particles dispersed in a polyurethane. For example, in some embodiments, the protein polyurethane alloys can be free of or substantially free of protein particles having an average diameter of greater than 1 micron (pm).
[0050] In some embodiments, the protein polyurethane alloys can be free of or substantially free of soy protein particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of or substantially free of collagen particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of or substantially free of gelatin particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of or substantially free of bovine serum albumin particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of or substantially free of pea protein particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of or substantially free of egg white albumin particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of or substantially free of casein protein particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of or substantially free of peanut protein particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of or substantially free of edestin protein particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of or substantially free of whey protein particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of or substantially free of karanja protein particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of, or substantially free of, cellulase particles having an average diameter of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of, or substantially free of, recombinant collagen fragment particles having an average diameter
of greater than 1 micron (pm). In some embodiments, the protein polyurethane alloys can be free of, or substantially free of, hemp protein particles having an average diameter of greater than 1 micron (pm).
[0051] In some embodiments, the proteins for use in coatings comprising a protein polyurethane alloy can be succinylated proteins. A succinylated protein is a protein modified with the addition of a succinyl group to a side chain of an amino acid in the protein. Most commonly, the succinyl group is added to lysine side chains. The method of adding a succinyl group to a side chain of an amino acid in a protein is commonly referred to as protein succinylation. Addition of succinyl groups on a protein can alter the protein’s functional and structural properties. In some cases, the addition of a relatively large modification like a succinyl moiety can be expected to alter the tertiary structure of the protein. Further, with the addition of a succinyl moiety, a lysine side chain can be altered from a primary amine to an acid, making it more hydrophilic, and can change its charge from positive to negative in physiological pH. Succinylation can be accomplished using techniques and chemistry well known the art.
[0052] A succinylated protein for use in the polyurethane alloys disclosed herein can be a protein containing lysine. In some embodiments, the succinylated protein can be a succinylated soy protein. In some embodiments, the succinylated protein can be a succinylated soy protein isolate. In some embodiments, the succinylated protein can be a succinylated collagen. In some embodiments, the succinylated protein can be a succinylated gelatin. In some embodiments, the succinylated protein can be succinylated bovine serum albumin. In some embodiments, the succinylated protein can be a succinylated pea protein. In some embodiments, the succinylated protein can be succinylated egg white albumin. In some embodiments, the succinylated protein can be a succinylated casein protein. In some embodiments, the succinylated protein can be a succinylated peanut protein. In some embodiments, the succinylated protein can be a succinylated edestin protein. In some embodiments, the succinylated protein can be a succinylated whey protein. In some embodiments, the succinylated protein can be a succinylated karanja protein. In some embodiments, the succinylated protein can be a succinylated cellulase. In some embodiments, the succinylated protein can be a succinylated hemp protein.
[0053] In some embodiments, the succinylated protein can have a solubility in water, measured as described below, of about 50% to about 100%, including subranges. For
example, in some embodiments, the succinylated protein can have a solubility in water of about 50% to about 100%, about 51% to about 100%, about 52% to about 100%, about 53% to about 100%, about 54% to about 100%, about 55% to about 100%, about 56% to about 100%, about 57% to about 100%, about 58% to about 100%, about 59% to about 100%, about 60% to about 100%, about 61% to about 100%, about 62% to about 100%, about 63% to about 100%, about 64% to about 100%, about 65% to about 100%, about 66% to about 100%, about 67% to about 100%, about 68% to about 100%, about 69% to about 100%, about 70% to about 100%, about 71% to about 100%, about 72% to about 100%, about 73% to about 100%, about 74% to about 100%, about 75% to about 100%, about 76% to about 100%, about 77% to about 100%, about 78% to about 100%, about 79% to about 100%, about 80% to about 100%, about 81% to about 100%, about 82% to about 100%, about 83% to about 100%, about 84% to about 100%, about 85% to about 100%, about 86% to about 100%, about 87% to about 100%, about 88% to about 100%, about 89% to about 100%, about 90% to about 100%, about 91% to about 100%, about 92% to about 100%, about 93% to about 100%, about 94% to about 100%, or about 95% to about 100%, or within a range having any two of these values as endpoints, inclusive of the endpoints.
[0054] In some embodiments, the succinylated protein can have a solubility in water of about 60% to about 90%, 61% to about 90%, about 62% to about 90%, about 63% to about 90%, about 64% to about 90%, about 65% to about 90%, about 66% to about 90%, about 67% to about 90%, about 68% to about 90%, about 69% to about 90%, about 70% to about 90%, about 71% to about 90%, about 72% to about 90%, about 73% to about 90%, about 74% to about 90%, about 75% to about 90%, about 76% to about 90%, about 77% to about 90%, about 78% to about 90%, about 79% to about 90%, about 80% to about 90%, about 81% to about 90%, about 82% to about 90%, about 83% to about 90%, about 84% to about 90%, or about 85% to about 90%. In still further embodiments, the succinylated protein can have a solubility in water of about 50%, about 51%, about 52%, about 53%, about 54%, about 55%, about 56%, about 57%, about 58%, about 59%, about 60%, about 61%, about 62%, about 63%, about 64%, about 65%, about 66%, about 67%, about 68%, about 69%, about 70%, about 71%, about 72%, about 73%, about 74%, about 75%, about 76%, about 77%, about 78%, about 79%, about 80%, about 81%, about 82%, about 83%, about 84%, about 85%, about 86%, about 87%, about 88%, about 89%, about
90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%, about 97%, about 98%, about 99%, or about 100%.
[0055] Unless otherwise specified, the solubility of a protein in water is measured according to the following method. The succinylated protein is suspended to a 5% (w/v) aqueous solution with DI water and the total solids are measured with a moisture analyzer. Then 35 mL of the 5% solution is centrifuged in a 50 mL tube for 10 minutes at 15,000 x g (times gravity). After centrifugation, the supernatant is decanted and the volume and total solids of the supernatant (soluble fraction) is measured. The solubility is then calculated as follows: solubility = (total solids of the supernatant * volume of the supernatant) / (Total solids of the 5% starting solution * volume of the 5% starting solution).
[0056] In some embodiments, the succinylated protein can have an average lysine modification, measured as specified below, of about 20% to about 100%, including subranges. For example, in some embodiments, the succinylated protein can have an average lysine modification of about 20% to about 100%, about 22% to about 100%, about 24% to about 100%, about 25% to about 100%, about 26% to about 100%, about 28% to about 100%, about 30% to about 100%, about 32% to about 100%, about 34% to about 100%, about 35% to about 100%, about 36% to about 100%, about 38% to about 100%, about 40% to about 100%, about 42% to about 100%, about 44% to about 100%, about 45% to about 100%, about 46% to about 100%, about 48% to about 100%, about 50 % to about 100%, about 52% to about 100%, about 54% to about 100%, about 55% to about 100%, about 56% to about 100%, about 58% to about 100%, about 60% to about 100%, about 62% to about 100%, about 64% to about 100%, about 65% to about 100%, about 66% to about 100%, about 68% to about 100%, about 70% to about 100%, about 72% to about 100%, about 74% to about 100%, about 75% to about 100%, about 76% to about 100%, about 78% to about 100%, about 80% to about 100%, about 82% to about 100%, about 84% to about 100%, about 85% to about 100%, about 86% to about 100%, about 88% to about 100%, about 90% to about 100%, about 92% to about 100%, about 94% to about 100%, or about 95% to about 100%, or within a range having any two of these values as endpoints, inclusive of the endpoints.
[0057] In some embodiments, the succinylated protein can have an average lysine modification of about 60% to about 90%, about 62% to about 90%, about 64% to about 90%, about 65% to about 90%, about 66% to about 90%, about 68% to about 90%, about
70% to about 90%, about 72% to about 90%, about 74% to about 90%, about 75% to about 90%, about 76% to about 90%, about 78% to about 90%, about 80% to about 90%, about 82% to about 90%, about 84% to about 90%, or about 85% to about 90%.
[0058] In some embodiments, the succinylated protein can have an average lysine modification of about 60% to about 80%, about 62% to about 80%, about 64% to about 80%, about 65% to about 80%, about 66% to about 80%, about 68% to about 80%, about 70% to about 80%, about 72% to about 80%, about 74% to about 80%, or about 75% to about 80%.
[0059] In still further embodiments, the succinylated protein can have an average lysine modification of about 20%, about 21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27%, about 28%, about 29%, about 30%, about 31%, about 32%, about 33%, about 34%, about 35%, about 36%, about 37%, about 38%, about 39%, about 40%, about 41%, about 42%, about 43%, about 44%, about 45%, about 46%, about 47%, about 48%, about 49%, about 50%, about 51%, about 52%, about 53%, about 54%, about 55%, about 56%, about 57%, about 58%, about 59%, about 60%, about 61%, about 62%, about 63%, about 64%, about 65%, about 66%, about 67%, about 68%, about 69%, about 70%, about 71%, about 72%, about 73%, about 74%, about 75%, about 76%, about 77%, about 78%, about 79%, about 80%, about 81%, about 82%, about 83%, about 84%, about 85%, about 86%, about 87%, about 88%, about 89%, about 90%, about 91%, about 92%, about 93%, about 94%, about 95%, about 96%, about 97%, about 98%, about 99%, or about 100%.
[0060] Unless otherwise specified, the average lysine modification for a succinylated protein disclosed herein is measured using the following lysine modification assay. A protein sample is digested using trypsin and loaded onto a liquid chromatography-mass spectrometer (LC/MS). After running the sample on the LC/MS, the sample is mapped by matching the digested peptides against the reference protein sequence for Beta- conglycinin alpha’ subunit (Gene CG-1; Organism: Glycine max (soybean) (Glycine hispida), which contains the possibility for both modified and unmodified lysine residues. Following peptide mapping, peak areas of matched peptides were used to calculate the proportion of modified to unmodified lysine at each lysine residue in the protein sequence and then the average % lysine modification was calculated based on all detected lysines. The following calculations are used to calculate the average % lysine modification. For each detected lysine, the lysine modification % was calculated as equal to the (SUM
succinylated lysine / (SUM succinylated lysine + SUM non-succinylated lysine). The overall average % lysine modification is then calculated by averaging the individual lysine modification % of all the detected lysines.
[0061] A protein for use in the protein polyurethane alloys disclosed herein can be a protein containing lysine. In some embodiments, the protein can be a soy protein. In some embodiments, the protein can be soy protein isolate. In some embodiments, the protein can be a collagen. In some embodiments, the protein can be gelatin. In some embodiments, the protein can be bovine serum albumin. In some embodiments, the protein can be pea protein. In some embodiments, the protein can be egg white albumin. In some embodiments, the protein can be casein protein. In some embodiments, the protein can be peanut protein. In some embodiments, the protein can be edestin protein. In some embodiments, the protein can be whey protein. In some embodiments, the protein can be karanja protein. In some embodiments, the protein can be hemp protein. In some embodiments, the protein can be an enzyme. In some embodiments, the protein can be cellulase.
[0062] Suitable polyurethanes for use in the coatings comprising the protein polyurethane alloy described herein include those that comprise at least two phases including a “soft phase” and a “hard phase.” The soft phase is formed from polyol segments within the polyurethane that separate from the urethane-containing phase due to differences in polarity. The urethane-containing phase is referred to as the hard phase. This phase separation is well known in the art and is the basis of the many of the properties of polyurethanes.
[0063] The soft phase is typically elastomeric at room temperature, and typically has a softening point or glass transition temperature (Tg) below room temperature. The Tg can be measured by Dynamic Mechanical Analysis (DMA) and quantified by either the peak of tan(6) or the onset of the drop in storage modulus. Alternately, Tg can be measured by Differential Scanning Calorimetry (DSC). In some cases, there can be crystallinity in the soft phase, which can be seen as a melting point, typically between 0 °C and about 60 °C.
[0064] The hard phase typically has a Tg or melting point above room temperature, more typically above about 80 °C. The softening of the hard phase can be measured by measuring the onset of the drop in storage modulus (sometimes referred to as stiffness) as measured by DMA.
[0065] The “soft phase” for the polyurethane or the protein polyurethane alloy including the polyurethane comprises the polyol component of the polyurethane. Its function is to be soft and flexible at temperatures above its Tg to lend toughness, elongation, and flexibility to the polyurethane. Typical soft segments can comprise polyether polyols, polyester polyols, polycarbonate polyols, and mixtures thereof. The soft segments typically range in molecular weight from about 250 D to greater than about 5 kD. The “hard phase” for the polyurethane or the protein polyurethane alloy including the polyurethane comprises the urethane segments of the polymer that are imparted by the isocyanate(s) used to connect the polyols along with short chain diols such as butane diol, propane diol, and the like. Typical isocyanates useful for the present polyurethanes include, but are not limited to, hexamethylene diisocyanate, isophorone diisocyanate, methylene diisocyanate, phenyl diisocyanate, and the like. These molecules are more polar and stiffer than the polyols used to make the soft segment. Therefore, the hard segment is stiffer and has a higher softening point compared to the soft segment. The function of the hard phase is to provide, among other properties, strength, temperature resistance, and abrasion resistance to the polyurethane.
[0066] In some embodiments described herein, the protein can be miscible with only the hard phase, leaving soft phase transitions substantially unaltered. Without wishing to be bound by particular theory, it is believed that when the protein is dissolved in the hard phase, it significantly increases the temperature at which the hard phase begins to soften, thus increasing the temperature resistance of the alloy.
[0067] In a protein polyurethane alloy including one or more miscible proteins and polyurethanes, the one or more proteins can be dissolved within the hard phase of the one or more polyurethanes. The protein polyurethane alloy can include at least one protein miscible with the hard phase of one or more polyurethanes in the alloy. In some embodiments, the protein polyurethane alloy can include a plurality of proteins and/or a plurality of polyurethane hard phases that are miscible with each other. In all of these embodiments, and without wishing to be bound by a particular theory, the protein, or plurality of proteins, is believed to be dissolved in the hard phase of the polyurethane, or plurality of polyurethanes.
[0068] One or more proteins dissolved within the hard phase of one or more polyurethanes can form a homogenous mixture when blended. In some embodiments, the protein polyurethane alloy can include a plurality of proteins dissolved within or more
polyurethanes such that the proteins and the polyurethane(s) form a homogenous mixture when blended and dried. Typically, the protein polyurethane alloy including a homogenous mixture of protein and polyurethane does not include a substantial amount of protein not dissolved in the polyurethane. That said, and in some embodiments, the protein polyurethane alloy can include a fraction of protein dispersed within the polyurethane.
[0069] In some embodiments, the protein polyurethane alloy can be transparent. In some embodiments, a transparent protein polyurethane alloy can indicate that the protein is miscible with the hard phase of the polyurethane in the alloy. As used herein, a “transparent” material means material having an opacity of about 50% or less. Opacity is measured by placing a sample of material over a white background to measure the Y tristimulus value (“Over white Y”) in reflectance with a spectrometer using the D65 10 degree illuminant. The same sample is then placed over a black background and the measurement is repeated, yielding “Over black Y”. Percent opacity is calculated as “Over black Y” divided by “Over white Y” times 100. 100% opacity is defined as lowest transparency and 0% opacity is defined as the highest transparency.
[0070] In some embodiments, the protein polyurethane alloy can be transparent and can have an opacity ranging from 0% to about 50%, including subranges. For example, the transparent protein polyurethane alloy, can have an opacity ranging from 0% to about 40%, 0% to about 30%, 0% to about 20%, 0% to about 10%, or 0% to about 5%. The transparency of the protein polyurethane alloy is evaluated before dying or otherwise coloring the protein polyurethane alloy.
[0071] A transparent protein polyurethane alloy can be created by selecting and blending the appropriate combination of one or more proteins and one or more polyurethanes. While not all combinations of protein and polyurethane will result in a transparent protein polyurethane alloy, it is within the skill of the ordinarily skilled artisan to identify whether a given blend results in a transparent protein polyurethane alloy in view of this disclosure. In embodiments directed to a coated fiber including a transparent protein polyurethane alloy described herein, the transparent protein polyurethane alloy can provide unique characteristics for the coated fiber. For example, compared to a nontransparent coating, the transparent protein polyurethane alloy can provide unique depth of color when dyed.
[0072] In some embodiments, the protein polyurethane alloy can include one or more coloring agents. In some embodiments, the coloring agent can be a colored dye, for example a fiber reactive dye, a direct dye, an acid dye, or a natural dye. Exemplary dyes, include but are not limited to, Azo structure acid dyes, metal complex structure acid dyes, anthraquinone structure acid dyes, and azo/diazo direct dyes. In some embodiments, the coloring agent can be pigment, for example a lake pigment.
[0073] Suitable polyurethanes according to embodiments described herein include, but are not limited to, aliphatic polyurethanes, aromatic polyurethanes, bio-based polyurethanes, or acrylic acid modified polyurethanes. Suitable polyurethanes are commercially available from manufacturers including Lubrizol, Hauthaway, Stahl, and the like. In some embodiments, a polyurethane for a protein polyurethane alloy can be bio-polyurethane. In some embodiments, the polyurethane is a water-dispersible polyurethane. In some embodiments, the polyurethane can be a polyester polyurethane. In some embodiments, the polyurethane can be a polyether polyurethane. In some embodiments, the polyurethane can be a polycarbonate-based polyurethane. In some embodiments, the polyurethane can be an aliphatic polyester polyurethane. In some embodiments, the polyurethane can be an aliphatic polyether polyurethane. In some embodiments, the polyurethane can be an aliphatic polycarbonate polyurethane. In some embodiments, the polyurethane can be an aromatic polyester polyurethane. In some embodiments, the polyurethane can be an aromatic polyether polyurethane. In some embodiments, the polyurethane can be an aromatic polycarbonate polyurethane.
[0074] In some embodiments, the polyurethane can have a soft segment selected from the group consisting of: polyether polyols, polyester polyols, polycarbonate polyols, and mixtures thereof. In some embodiments, the polyurethane can have a hard segment comprising diisocyanates and optionally short chain diols. Suitable diisocyanates can be selected from the group consisting of: aliphatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate; aromatic diisocyanates such as 4,4’ diphenyl methylene diisocyanate, toluene diisocyanate, phenyl diisocyanate, and mixtures thereof. Suitable short chain diols include ethylene glycol, propane diol, butane diol, 2,2 methyl 1,3 propane diol, pentane diol, hexane diol and mixtures thereof. In some embodiments crosslinkers such as multifunctional alcohols, for example, trimethylol propane triol, or diamines such as ethylene diamine or 4,4’diamino, diphenyl diamine.
[0075] Exemplary commercial polyurethanes, include but are not limited to L3360 and Hauthane HD-2001 available from C.L. Hauthaway & Sons Corporation, SANCURE™ polyurethanes available from Lubrizol Corporation, BONDTHANE™ polyurethanes, for example UD-108, UD-250, and UD-303 available from Bond Polymers International, EPOTAL® ECO 3702 and EPOTAL® Pl 00 ECO from BASF, and Permutex Evo EX-RC- 2214 (RC-2214) from Stahl. L3360 is a aliphatic polyester polyurethane polymer aqueous dispersion having a 35% solids content, a viscosity of 50 to 500 cps (centipoise), and a density of about 8.5 Ib/gal (pounds per gallon). HD-2001 is an aliphatic polyester polyurethane polymer aqueous dispersion having a 40% solids content, a viscosity of 50 to 500 cps, and a density of about 8.9 Ib/gal. BONDTHANE™ UD-108 is an aliphatic polyether polyurethane polymer aqueous dispersion having a 33% solids content, a viscosity of 300 cps, and a density of 8.7 Ib/gal. BONDTHANE™ UD-250 is an aliphatic polyester polyurethane polymer aqueous dispersion having a 35% solids content, a viscosity of 200 cps, and a density of 8.8 Ib/gal. BONDTHANE™ UD-303 is an aliphatic poly ether polyurethane polymer aqueous dispersion having a 35% solids content, a viscosity of less than 500 cps, and a density of 8.7 Ib/gal. EPTOAL® P100 ECO is a polyester polyurethane elastomer aqueous dispersion having approximately 40% solids and a viscosity of about 40 mPas. RC-2214 is an aliphatic polyether polyurethane polymer aqueous dispersion having a 58-60% solids content, a viscosity of 4,000 to 15,000 cps, and a density of about 8.9 Ib/gal.
[0076] Exemplary bio-based polyurethanes include, but are not limited to, L3360 available from C.L. Hauthaway & Sons Corporation, IMPRANIL® Eco DLS, IMPRANIL® Eco DL 519, IMPRANIL® Eco DLP-R, and IMPRAPERM® DL 5249 available from Covestro. IMPRANIL® Eco DLS is an anionic, aliphatic polyester polyurethane polymer aqueous dispersion having approximately 50% solids content, a viscosity of less than 1,200 MPa s, and a density of about 1.1 g/cc. IMPRANIL® Eco DL 519 is an anionic, aliphatic polyester polyurethane polymer aqueous dispersion. IMPRANIL® Eco DLP-R is an anionic, aliphatic polyester polyurethane polymer aqueous dispersion. IMPRAPERM® DL 5249 is an anionic aliphatic polyester-polyurethane polymer aqueous dispersion.
[0077] In some embodiments, the polyurethane can include reactive groups that can be cross-linked with a protein. Exemplary reactive groups include, but are not limited to, a sulfonate, an aldehyde, a carboxylic acid or ester, a blocked isocyanate, or the like, and
combinations thereof. In such embodiments, the polyurethane can be crosslinked to the protein in the protein polyurethane alloy through the reaction of a reactive group on the protein with the reactive group present in the polyurethane.
[0078] Suitable proteins according to embodiments described herein include, but are not limited to, collagen, gelatin, bovine serum albumin (BSA), soy proteins, pea protein, egg white albumin, casein, peanut protein, edestin protein, whey protein, karanja protein, cellulase, and hemp. Suitable collagens include, but are not limited to, recombinant collagen (r-Collagen), a recombinant collagen fragment, and extracted collagens. Suitable soy proteins include, but are not limited to, soy protein isolate (SPI), soymeal protein, and soy protein derivatives. In some embodiments, the soy protein isolate can be partially hydrolyzed soy protein isolate. Suitable pea proteins include, but are not limited to, pea protein isolate, and pea protein derivatives. In some embodiments, the pea protein isolate can be partially hydrolyzed pea protein isolate.
[0079] Table 1 below lists some exemplary proteins. The gelatin is gelatin from porcine skin, Type A (Sigma Aldrich G2500). The collagen is extracted bovine collagen purchased from Wuxi BIOT Biology-technology Company. The bovine serum albumin Sigma Aldrich 5470 bovine serum albumin. The r-Collagen is recombinant collagen from Modem Meadow. The soy protein isolate is soy protein isolate purchased from MP Medicals (IC90545625). The pea protein is pea protein powder purchased from Bobs Red Mills (MTX5232). The egg white albumin protein is albumin from chicken egg white (Sigma Aldrich A5253). The casein protein is casein from bovine milk (Sigma Aldrich C7078). The peanut protein is peanut protein powder purchased from Tru-Nut. The whey protein is whey from bovine milk (Sigma Aldrich W1500). Other suitable soy protein isolates include, but are not limited to, soy protein isolate purchased from AMD (Clarisoy 100, 110, 150, 170, 180), or DuPont (SUPRO® XT 55, SUPRO® XT 221D, SUPRO® XT 221D-IP, and SOB IND® Balance). Other suitable pea protein powders include, but are not limited to, pea protein powder purchased from Puris (870 and 870H).
[0080] Karanja protein is a protein found in Karanja seeds harvested from Pongamia pinnata trees (also known as Pongamia glabra trees). See Rahman, M., and Netravali, “Green Resin from Forestry Waste Residue ‘Karanja (Pongamia pinnata) Seed Cake’ for Biobased Composite Structures,” ACS Sustainable Chem. Eng., 2: 2318-2328 (2014); see also Mandal et al., “Nutritional Evaluation of Proteins from three Non-traditional Seeds with or without Amino Acids Supplementation in Albino Rats,” Proc. Indian natn. Sci.
Acad., B50, No. 1, 48-56 (1984). The protein can be extracted from Karanja seeds using a solvent extraction process. Id. In some embodiments, the karanja protein can be karanja protein isolate. In such embodiments, karanja protein isolate can be obtained by alkaline extraction and acid precipitation of defatted karanja seed cake. See Rahman, M., and Netravali, “Green Resin from Forestry Waste Residue ‘Karanja (Pongamia pinnata) Seed Cake’ for Biobased Composite Structures,” ACS Sustainable Chem. Eng., 2: 2318-2328 (2014).
[0081] Suitable cellulase proteins are listed below in Table 1. The “Cellulase-RG” protein is Native Trichoderma sp. Cellulase available from CREATIVE ENZYMES®. The “Cellulase-IG” protein is laboratory grade cellulase available from Carolina Biological Supply Company.
[0082] The 50 KDa recombinant collagen fragment (50 KDa r-Collagen fragment) in Table 1 is a collagen fragment comprising the amino acid sequence listed as SEQ ID NO: 1.
[0083] The “dissolution method” listed in Table 1 is an exemplary aqueous solvent in which the protein can be dissolved in a solution that is miscible with the hard phase of the polyurethane as described herein. Proteins that can be at least partly dissolved in an aqueous solution are suitable for forming protein polyurethane alloys with polyurethane dispersions.
[0084] In some embodiments, the protein can have one or more of the following properties: (i) a molecular weight within a range described herein (ii) an isoelectric point within a range described below, (iii) an amino acid composition measured in grams of lysine per 100 grams of protein in a range described below, and (iv) protein thermostability up to 200 °C.
Protein Molecular Weight
[0085] In some embodiments, the protein suitable for blending with the polyurethane can have a molecular weight ranging from about 1 KDa to about 700 KDa, including subranges. For example, the protein can have a molecular weight ranging from about 1 KDa to about 700 KDa, about 10 KDa to about 700 KDa, about 20 KDa to about 700 KDa, about 50 KDa to about 700 KDa, about 100 KDa to about 700 KDa, about 200 KDa to about 700 KDa, about 300 KDa to about 700 KDa, about 400 KDa to about 700 KDa,
about 500 KDa to about 700 KDa, about 600 KDa to about 700 KDa, about 1 KDa to about 600 KDa, about 1 KDa to about 500 KDa, about 1 KDa to about 400 KDa, about 1 KDa to about 300 KDa, about 1 KDA to about 200 KDa, about 1 KDa to about 100 KDa, about 1 KDa to about 50 KDa, about 1 KDa to about 20 KDa, or about 1 KDa to about 10 KDa, or within a range having any two of these values as endpoints, inclusive of the endpoints.
Protein Isoelectric Point
[0086] In some embodiments, the protein suitable for blending with the polyurethane can have an isoelectric point ranging from about 4 to about 10, including subranges. For example, the protein can have an isoelectric point ranging from about 4 to about 10, about 4.5 to about 9.5, about 5 to about 9, about 5.5 to about 8.5, about 6 to about 8, about 6.5 to about 7.5, or about 6.5 to about 7, or within a range having any two of these values as endpoints, inclusive of the endpoints. In some embodiments, the protein can have an isoelectric point ranging from about 4 to about 5.
Protein Amino Acid Composition
[0087] In some embodiments, the protein suitable for blending with the polyurethane can have an amino acid composition measured in grams of lysine per 100 grams of protein (as referred to as a “lysine weight percent”) ranging from about 0.5 wt% to about 100 wt%, including subranges. For example, the protein can have a lysine weight percent ranging from about 0.5 wt% to about 100 wt%, about 1 wt% to about 100 wt%, about 5 wt% to about 100 wt%, about 10 wt% to about 100 wt%, about 20 wt% to about 100 wt%, about 30 wt% to about 100 wt%, about 40 wt% to about 100 wt%, about 50 wt% to about 100 wt%, about 60 wt% to about 100 wt%, about 70 wt% to about 100 wt%, about 80 wt% to about 100 wt%, or about 90 wt% to about 100 wt%, or within a range having any two of these values as endpoints, inclusive of the endpoints. In some embodiments, the protein can be a polylysine.
[0088] In some embodiments, the protein suitable for blending with the polyurethane can have a lysine weight percent ranging from about 0.5 wt% to about 20 wt%, including subranges. For example, the protein can have a lysine weight percent ranging from about 0.5 wt% to about 20 wt%, about 1 wt% to about 19 wt%, about 2 wt% to about 18 wt%, about 3 wt% to about 17 wt%, about 4 wt% to about 16 wt%, about 5 wt% to about 15
wt%, about 6 wt% to about 14 wt%, about 7 wt% to about 13 wt%, about 8 wt% to about 12 wt%, about 9 wt% to about 11 wt%, or about 9 wt% to about 10 wt%, or within a range having any two of these values as endpoints, inclusive of the endpoints. In some embodiments, the protein can have a lysine weight percent ranging from about 1 wt% to about 20 wt%. In some embodiments, the protein can have a lysine weight percent ranging from about 5 wt% to about 20 wt%. In some embodiments, the protein can have a lysine weight percent ranging from about 1 wt% to about 12 wt%. In some embodiments, the protein can have a lysine weight percent ranging from about 5 wt% to about 12 wt%. In some embodiments, the protein can have a lysine weight percent ranging from about 1 wt% to about 15 wt%. In some embodiments, the protein can have a lysine weight percent ranging from about 5 wt% to about 15 wt%.
[0089] In some embodiments, the protein suitable for blending with the polyurethane can be thermo-stable. In some embodiments, the protein can be non-thermo-stable. As described herein, protein thermo-stability is determined by a differential scanning calorimetry (DSC), where a pre-dried protein powder (with moisture less than 3%) is scanned from 0 °C to 200 °C. In the protein’s DSC curves, an endothermic peak larger than 10 mW/mg is determined to be a “denaturation peak”, and the temperature corresponding to the endothermic “denaturation peak” is defined as the “denaturation temperature” of the protein. A protein that is “thermo-stable” means that the protein has denaturation temperature of 200 °C or more. For purposes of the present disclosure, a protein with a denaturation temperature below 200 °C is considered “non-thermo-stable.”
Protein Dissolution
[0090] In some embodiments, before blending with one or more polyurethanes, one or more proteins can be dissolved in an aqueous solution to form an aqueous protein mixture. In some embodiments, dissolving the protein in an aqueous solution before blending the protein with one or more polyurethanes can facilitate miscibility of the protein with the hard phase of the one or more polyurethanes. For example, dissolving the protein in an aqueous solution before blending the protein with one or more polyurethanes can facilitate miscibility of the protein with the hard phase of the polyurethane(s). Not all proteins are naturally miscible with any phase of a polyurethane.
[0091] Suitable aqueous solutions include, but are not limited to, water, an aqueous alkali solution, an aqueous acid solution, an aqueous solution including an organic solvent, a
urea solution, and mixtures thereof. In some embodiments, the aqueous alkali solution can be a basic solution such as a sodium hydroxide, ammonia or ammonium hydroxide solution. In some embodiments, examples of an acidic aqueous solution can be an acetic acid or hydrochloric acid (HC1) solutions. Suitable organic solvents include, but are not limited to, ethanol, isopropanol, acetone, ethyl acetate, isopropyl acetate, glycerol, and the like. In some embodiments, the protein concentration in the aqueous protein mixture can range from about 10 g/L to about 300 g/L, including subranges.
[0092] In some embodiments, the amount of protein in the protein polyurethane alloy can range from about 5 wt% to about 50 wt% of protein, including subranges. For example, in some embodiments, the amount of protein in the polyurethane alloy can range from about 5 wt% to about 50 wt%, about 10 wt% to about 50 wt%, about 15 wt% to about 50 wt%, about 20 wt% to about 50 wt%, about 25 wt% to about 50 wt%, about 30 wt% to about 50 wt%, about 35 wt% to about 50 wt%, about 40 wt% to about 50 wt%, about 45 wt% to about 50 wt%, about 5 wt% to about 45 wt%, about 5 wt% to about 40 wt%, about 5 wt% to about 35 wt%, about 5 wt% to about 30 wt%, about 5 wt% to about 25 wt%, about 5 wt% to about 20, about 5 wt% to about 15 wt%, or about 5 wt% to about 10 wt% or within a range having any two of these values as endpoints, inclusive of the endpoints. In some embodiments, the amount of protein in the protein polyurethane alloy can range from about 20 wt% to about 35 wt%.
[0093] In some embodiments, the amount of polyurethane in the protein polyurethane alloy can range from about 50 wt% to about 95 wt%, including subranges. For example, in some embodiments, the amount of polyurethane in the protein polyurethane alloy can range from about 50 wt% to about 95 wt%, about 55 wt% to about 95 wt%, about 60 wt% to about 95 wt%, about 65 wt% to about 95 wt%, about 70 wt% to about 95 wt%, about 75 wt% to about 95 wt%, about 80 wt% to about 95 wt%, about 85 wt% to about 95 wt%, about 90 wt% to about 95 wt%, about 50 wt% to about 90 wt%, about 50 wt% to about 85 wt%, about 50 wt% to about 80 wt%, about 50 wt% to about 75 wt%, about 50 wt% to about 70 wt%, about 50 wt% to about 65 wt%, about 50 wt% to about 60 wt%, or about 50 wt% to about 55 wt%, or within a range having any two of these values as endpoints, inclusive of the endpoints. In some embodiments, the amount of polyurethane in the protein polyurethane alloy can range from about 65 wt% to about 80 wt%.
[0094] Any of the above-listed ranges for the weight percentages of protein and polyurethane in the protein polyurethane alloy can be combined. For example, in some
embodiments, the weight percentages of protein and polyurethane in the protein polyurethane alloy can be any of the following. The amount of protein in the polyurethane alloy can range from about 5 wt% to about 50 wt% and the amount of polyurethane in the protein polyurethane alloy can range from about 50 wt% to about 95 wt%. The amount of protein in the polyurethane alloy can range from about 15 wt% to about 50 wt% and the amount of polyurethane in the protein polyurethane alloy can range from about 50 wt% to about 85 wt%. The amount of protein in the polyurethane alloy can range from about 20 wt% to about 50 wt% and the amount of polyurethane in the protein polyurethane alloy can range from about 50 wt% to about 80 wt%. The amount of protein in the polyurethane alloy can range from about 25 wt% to about 50 wt% and the amount of polyurethane in the protein polyurethane alloy can range from about 50 wt% to about 75 wt%. The amount of protein in the polyurethane alloy can range from about 30 wt% to about 50 wt% and the amount of polyurethane in the protein polyurethane alloy can range from about 50 wt% to about 70 wt%. The amount of protein in the polyurethane alloy can range from about 10 wt% to about 40 wt% and the amount of polyurethane in the protein polyurethane alloy can range from about 60 wt% to about 90 wt%. The amount of protein in the polyurethane alloy can range from about 15 wt% to about 40 wt% and the amount of polyurethane in the protein polyurethane alloy can range from about 60 wt% to about 85 wt%. The amount of protein in the polyurethane alloy can range from about 20 wt% to about 40 wt% and the amount of polyurethane in the protein polyurethane alloy can range from about 60 wt% to about 80 wt%. The amount of protein in the polyurethane alloy can range from about 20 wt% to about 35 wt% and the amount of polyurethane in the protein polyurethane alloy can range from about 65 wt% to about 80 wt%. In some embodiments, the above-listed weight percent values and ranges can be based on the total weight of the protein polyurethane alloy. In some embodiments, the above-listed weight percent values and ranges can be based on the total weight of only protein and polyurethane in a protein polyurethane alloy. Unless otherwise specified, a weight percent value or range for the polyurethane and the protein is based on the total weight of only protein and polyurethane in a protein polyurethane alloy.
[0095] In some embodiments, the sum of the amount of protein plus the amount of polyurethane in the protein polyurethane alloy can be about 80 wt% or more. For example, in some embodiments, the sum of the amount of protein plus the amount of polyurethane in the protein polyurethane alloy can range from about 80 wt% to 100 wt%,
about 82 wt% to 100 wt%, about 84 wt% to 100 wt%, about 86 wt% to 100 wt%, about 88 wt% to 100 wt%, about 90 wt% to 100 wt%, about 92 wt% to 100 wt%, about 94 wt% to 100 wt%, about 96 wt% to 100 wt%, or about 98 wt% to 100 wt%.
[0096] In some embodiments, the protein polyurethane alloy can include water making up a portion of the total weight percent of the material. In some embodiments, the amount of water in the protein polyurethane alloy can range from about 1 wt% to about 10 wt%, including subranges. For example, in some embodiments, the amount of water in the protein polyurethane alloy can range from about 1 wt% to about 10 wt%, about 2 wt% to about 10 wt%, about 3 wt% to about 10 wt%, about 4 wt% to about 10 wt%, about 5 wt% to about 10 wt%, about 6 wt% to about 10 wt%, about 7 wt% to about 10 wt%, about 8 wt% to about 10 wt%, about 1 wt% to about 9 wt%, about 1 wt% to about 8 wt%, about 1 wt% to about 7 wt%, about 1 wt% to about 6 wt%, about 1 wt% to about 5 wt%, about 1 wt% to about 4 wt%, or about 1 wt% to about 3 wt%, or within a range having any two of these values as endpoints, inclusive of the endpoints.
[0097] In some embodiments, the protein polyurethane alloy can be a protein polyurethane alloy as descried in U.S. Pub. No. 2021/0355326, which is hereby incorporated by reference in its entirety.
[0098] Coated fibers according to embodiments described herein can comprise a core fiber and a coating disposed over the core fiber and comprising a protein dissolved within a polyurethane.
[0099] FIG. 1 shows a coated fiber 100 according to some embodiments. Coated fiber 100 comprises a core fiber 110 and a coating 120 coated on core fiber 110. Coating 120 can comprise one or more protein polyurethane alloys as described herein. Coating 120 can be coated around all or a portion of core fiber 110. In other words, coating 120 can be coated around all or a portion of an outer surface 112 of core fiber 110. In some embodiments, coating 120 can be coated around the entirety of core fiber 110. In such embodiments, core fiber 110 can be surrounded by coating 120.
[0100] In some embodiments, coating 120 can be disposed over core fiber 110. For example, coating 120 can be disposed over outer surface 112 of core fiber 110. In some embodiments, coating 120 can be disposed on core fiber 110. For example, coating 120 can be disposed on outer surface 112 of core fiber 110.
[0101] Core fiber 110 can comprise one or more fiber materials. Suitable fiber materials for core fiber 110 include, but are not limited to natural fiber materials, for example
cotton, linen, silk, wool, kenaf, flax, cashmere, angora, bamboo, bast, hemp, soya, seacell, milk or milk proteins, spider silk, chitosan, mycelium, cellulose including bacterial cellulose, or wood. Additional suitable fiber materials for core fiber 110 include, but are not limited to, synthetic fiber materials, for example polyesters, nylons, aromatic polyamides, or polyolefins such as polyethylene, polypropylene. In some embodiments, core fiber 110 can comprise a cellulosic material like rayon, lyocell (for example, TENCEL™), modal, viscose, SORBTEK®, elastomers such as LYCRA®, spandex (for example, DORLASTAN®), or ELASTANE®, polyester-polyurethane copolymers, or aramids. In some embodiments, core fiber 110 can comprise a polymeric fiber with functional particles in the polymer. Exemplary functional particles include ceramic particles mixed in a polymeric resin during an extrusion process for making the polymeric fibers. Such ceramic particles can provide the polymeric fibers with desirable heat dissipation and flame resistance properties. In some embodiments, core fiber 110 can comprise fiber made of fruit pulp (e.g., grape pulp or apple pulp) or a pineapple fiber. In some embodiments, core fiber 110 can comprise fiber made from recycled materials, for example, recycled plastics. In some embodiments, core fiber 110 can comprise algae. In some embodiments, core fiber 110 can comprise cork.
[0102] In some embodiments, coated fiber 100 can comprise a coloring agent. In some embodiments, the coloring agent can be a dye. Suitable dyes include, but are not limited to, a fiber reactive dye, an acid dye, a direct dye, or a natural dye. Exemplary dyes, include but are not limited to, Azo structure acid dyes, metal complex structure acid dyes, anthraquinone structure acid dyes, and azo/diazo direct dyes.
[0103] In some embodiments, core fiber 110 can comprise the coloring agent. In some embodiments, coating 120 can comprise the coloring agent. In some embodiments, core fiber 110 and coating 120 can comprise the coloring agent.
[0104] In some embodiments, coated fiber 100 can have coating uptake of greater than or equal to 10%. “Coating uptake” defines the mass of coating 120 coated on core fiber 110 relative to the mass of core fiber 110. A coating uptake (U) is defined by Equation 1 below, where Mi is the mass of core fiber 110 before coating 120 is applied and M2 is the mass coated fiber 100. (Equation 1)
[0105] In some embodiments, coated fiber 100 can have a coating uptake of greater than or equal to 15%. In some embodiments, coated fiber 100 can have a coating uptake of greater than or equal to 20%. In some embodiments, coated fiber 100 can have a coating uptake of greater than or equal to 25%. In some embodiments, coated fiber 100 can have a coating uptake of greater than or equal to 30%. In some embodiments, coated fiber 100 can have a coating uptake of greater than or equal to 40%. In some embodiments, coated fiber 100 can have a coating uptake of greater than or equal to 50%. In some embodiments, coated fiber 100 can have a coating uptake of greater than or equal to 60%. In some embodiments, coated fiber 100 can have a coating uptake of greater than or equal to 70%. In some embodiments, coated fiber 100 can have a coating uptake of greater than or equal to 80%.
[0106] In some embodiments, coated fiber 100 can have a coating uptake ranging from about 10% to about 100%, including subranges. For example, in some embodiments, coated fiber 100 can have a coating uptake ranging from about 15% to about 100%, about 20% to about 100%, about 25% to about 100%, about 30% to about 100%, about 40% to about 100%, about 50% to about 100%, about 60% to about 100%, about 70% to about 100%, about 80% to about 100%, about 10% to about 90%, about 10% to about 80%, about 10% to about 70%, about 10% to about 60%, about 10% to about 50%, about 10% to about 40%, about 10% to about 30%, about 10% to about 25%, or about 10% to about 20%, or within a range having any two of these values as endpoints, inclusive of the endpoints. In some embodiments, coated fiber 100 can have a coating uptake ranging from about 10% to about 110%.
[0107] In some embodiments, coating 120 can have a thickness 122, measured from outer surface 112 of core fiber to an outer surface of coating 120, of greater than or equal to about 100 nanometers. In some embodiments, thickness 122 can be greater than or equal to about 500 nanometers. In some embodiments, thickness 122 can be greater than or equal to about 1 micrometer (micron). In some embodiments, thickness 122 can be greater than or equal to about 10 microns.
[0108] In some embodiments, thickness 122 can range from about 100 nanometers to about 1 millimeter, including subranges. For example, thickness 122 can range from about 500 nanometers to about 1 millimeter, about 1 micron to about 1 millimeter, about 100 nanometers to about 10 microns, or about 100 nanometers to about 1 micron, or within a range having any two of these values as endpoints.
[0109] In some embodiments, thickness 122 can be greater than or equal to 1% of an effective diameter 114 of core fiber 110. In some embodiments, thickness 122 can be greater than or equal to 2% of effective diameter 114 of core fiber 110. In some embodiments, thickness 122 can be greater than or equal to 5% of effective diameter 114 of core fiber 110.
[0110] In some embodiments, effective diameter 114 of core fiber 110 can be greater than or equal to about 0.01 millimeters. In some embodiments, effective diameter 114 of core fiber 110 can range from about 0.01 millimeters to about 10 millimeters.
[OHl] In some embodiments, a portion of coating 120 can be integrated into core fiber 110. In such embodiments, a first portion of coating 120 can be integrated into core fiber 110 and a second portion of coating 120 can define a coating layer on outer surface 112 of core fiber 110. The coating layer can have a thickness 122 as discussed above for coating 120.
[0112] Core fiber 110 can have any suitable cross-sectional shape. For example, the cross-sectional shape of core fiber 110 can be a square, a rectangle, a triangle, a circle, an ellipse, an oval, a pentagon, an octagon, or a star-shape. FIG. 2 illustrates core fiber 110 having a star-shaped cross section according to some embodiments.
[0113] In some embodiments, coating 120 can be a single continuous coating on core fiber 110. In such embodiments, coating 120 can be a single coating surrounding all or a portion of core fiber 110. In other embodiments, coating 120 can be a discontinuous coating comprising a plurality of discrete coating portions 124 disposed around core fiber 110. In such embodiments, coating 120 can comprise any suitable number of discrete coating portions 124, for example, two, three, four, five, six, seven, eight, or more coating portions. FIG. 3 illustrates a cross-section of a coated fiber comprising three discrete coating portions 124 on core fiber 110 according to some embodiments. FIG. 4 illustrates a cross-section of a coated fiber comprising six discrete coating portions 124 on core fiber 110 according to some embodiments. FIG. 5 illustrates a cross-section of a coated fiber comprising two discrete coating portions 124 on core fiber 110 according to some embodiments.
[0114] In some embodiments, coating 120 can be a partial coating surrounding only a portion of core fiber 110. In such embodiments, coating 120 does not surround the entirety of core fiber 110. For example, coating 120 can be partial coating surrounding about 50% of core fiber 110. As another example, coating 120 can be a partial coating
surrounding about 75% of core fiber 110. FIG. 6 illustrates a cross-section of a coated fiber comprising a partial coating 120 according to some embodiments. FIG. 7 illustrates a cross-section of a coated fiber comprising a partial coating 120 according to some embodiments.
[0115] In some embodiments, one or more coated fibers 100 can be formed into a fabric or textile material using a technique such as weaving, knitting, spreading, felting, stitching, and/or crocheting. In such embodiments, a first coated fiber 100 can be in contact with itself and/or a second coated fiber 100 at one or more points and can slide over itself and/or the second coated fiber 100 in at least one direction. In some embodiments, one or more coated fibers 100 and one or more fibers not coated with a protein polyurethane alloy can be formed into a fabric or textile material using a technique such as weaving, knitting, spreading, felting, stitching, and/or crocheting. In such embodiments, a coated fiber 100 can be in contact with itself and/or a fiber not coated with a protein polyurethane alloy at one or more points and can slide over itself and/or the fiber not coated with a protein polyurethane alloy in at least one direction.
[0116] In some embodiments, a plurality of coated fibers 100 can be formed into a nonwoven fabric or textile material. In such embodiments, the coated fibers can be mechanically, chemically, or thermally bound to each other at some points and can still slide over each other in at least one direction at one or more positions within the material. In some embodiments, one or more coated fibers 100 and one or more fibers not coated with a protein polyurethane alloy can be formed into a non-woven fabric or textile material. In such embodiments, a coated fiber can be mechanically, chemically, or thermally bound to itself and/or a fiber not coated with a protein polyurethane alloy at some points and can still slide over itself and/or the fiber not coated with a protein polyurethane alloy in at least one direction at one or more positions within the material.
[0117] The ability of one or more coated fibers and/or fibers not coated with a protein polyurethane alloy to slide relative to each other facilitates flexibility in a material. In contrast, coating a surface of a fabric or textile material with a protein polyurethane alloy using, for example, a dipping process, a spraying process, or a roll-to-roll coating process can fix the fibers in a planar direction, which can prevent or inhibit the ability of the fibers to slide over one another. By fixing the fibers in a planar direction, haptic and/or drape properties can be affected.
[0118] In some embodiments, the amount of coating disposed on coated fibers within a fabric or textile material can be uniform through a cross-sectional thickness of the material. In such embodiments, all the coated fibers within the fabric or textile material can have a coating uptake that is substantially the same. As used herein, a coating uptake being “substantially the same” means that all the coated fibers within the fabric or textile material have an average coating uptake, the variation between the fiber with the highest coating uptake is no more than 10% higher than the average, and the variation between the fiber with the lowest coating uptake is no more than 10% lower than the average. For example, if all the coated fibers within the fabric or textile material have an average coating uptake of 50%, the fiber having the highest coating uptake can have a coating uptake of no higher than 55% and the fiber having the lowest coating uptake can have a coating uptake of no lower than 45%.
[0119] Coated fiber 100 can be made by a method comprising coating core fiber 110 with coating 120 comprising a protein polyurethane alloy. In some embodiments, the method of making coated fiber 100 can comprise applying a coating solution comprising the protein polyurethane alloy to core fiber 110 and drying the coated core fiber to form coated fiber 100. For example, in some embodiments, the method of making coated fiber 100 can comprise a dip coating process that comprises dipping core fiber 110 in the coating solution comprising the protein polyurethane alloy and drying the coated core fiber to form coated fiber 100.
[0120] In some embodiments, the method of making coated fiber 100 can comprise dying core fiber 110, coating 120, or both. In some embodiments, the method can comprise dying core fiber 110, coating 120, or both after coating 120 is coated on core fiber 110. In some embodiments, the method can comprise dying core fiber 110, coating 120, or both before coating 120 is coated on core fiber 110. In some embodiments, dying coating 120 before coating 120 is coated on core fiber 110 can comprise adding a dye to the coating solution comprising the protein polyurethane alloy.
[0121] In some embodiments, the coating solution comprising the protein polyurethane alloy can be formed by blending one or more proteins with one or more water-borne polyurethane dispersions in a liquid state. In some embodiments, the coating solution comprising the protein polyurethane alloy can be formed by blending one or more proteins dissolved or dispersed in an aqueous solution with one or more water-borne polyurethane dispersions in a liquid state. In some embodiments, the polyurethane
dispersion can be ionic, and either anionic or cationic. In some embodiments, the polyurethane dispersion can be nonionic.
[0122] In some embodiments, one or more additives can be added to the coating solution. The additive(s) can influence the final properties of coating 120, coated fiber 100, or both. For example, the additive(s) added can impact one or more of the following material properties of coating 120, coated fiber 100, or both: stiffness, elasticity, cohesive strength, tear strength, fire retardancy, chemical stability, or wet stability. Suitable additives include, but are not limited to, cross-linkers, fillers, dyes, pigments, plasticizers, waxes, rheological modifiers, flame retardants, antimicrobial agents, antifungal agents, antioxidants, UV stabilizers, mechanical foaming agents, chemical foaming agents, foam stabilizers, and the like. Suitable dyes include, but are not limited, to fiber reactive dyes or natural dyes. Suitable cross-linkers include, but are not limited to, epoxy -based crosslinkers, (for example, poly(ethylene glycol) diglycidyl ether (PEGDE) available from Sigma Aldridge), isocyanate-based cross-linkers (for example, X-Tan® available from Lanxess), and carbodiimide-based cross-linkers. Suitable foaming agents include, HeiQ Chemtex 2216-T (a stabilized blend of nonionic and anionic surfactants), HeiQ Chemtex 2241 -A (a modified HEUR (hydrophobically-modified ethylene oxide urethane) thickener), HeiQ Chemtex 2243 (a non-ionic silicone dispersion), or HeiQ Chemtex 2317 (a stabilized blend of nonionic and anionic surfactants) foam stabilizers available from HeiQ Chemtex. Suitable antimicrobial/antifungal agents include Ultra-Fresh DW-56, or other antimicrobial/antifungal agents used in the leather industry. Suitable flame retardants include Cetaflam® DB9 (organophosphorous compounds containing C-PO(OH)2 or C-PO(OR)2 groups with the carbon chain containing polymers), Cetaflam® PD3300 (organophosphorous compounds containing C~PO(OH)2 or C-PO(OR)2 groups with the carbon chain containing polymers), or other flame retardants used for coated textiles. Suitable fillers include, but are not limited to, thermoplastic microspheres, for example, Expancel® Microspheres. Suitable rheological modifiers include, but are not limited to, alkali swellable rheological modifiers, hydrophobically- modified ethylene oxide-based urethane (HEUR) rheological modifiers, and volume exclusion thickeners. Exemplary alkali swellable rheological modifiers include but are not limited to, Acrysol™ DR-106, Acrysol™ ASE-60 from Dow Chemicals, Texicryl® 13-3131, and Texicryl® 13-308 from Scott-Bader. Exemplary HEUR modifiers include, but are not limited to, RM-4410 from Stahl and Chemtex 2241 -A from HeiQ. Exemplary
volume exclusion thickeners include, but are not limited to, Walocel™ XM 20000 PV from Dow Chemicals and Methyl-Hydroxyethyl Cellulose from Sigma- Aldrich.
[0123] In some embodiments, a fabric or textile material can be made by coating one or more core fibers with a coating comprising a protein dissolved within a polyurethane to form one or more coated fibers 100, and after forming the one or more coated fibers 100, mechanically entangling the one or more coated fibers 100 to form the fabric or textile material. Exemplary mechanical entangling techniques include, but are not limited to, weaving, knitting, spreading, felting, stitching, crocheting, or any other similar technique for making a fabric or textile material.
[0124] The embodiments discussed herein will be further clarified in the following examples. It should be understood that these examples are not limiting to the embodiments described above.
EXAMPLE 1
[0125] A soy protein isolate (SPI) solution was prepared by dissolving 3.75 g of SPI (SUPRO® XT 221D-IP; DuPont; available from Solae LLC) in 21.25 mL of a 0.05 mol/L NaOH (sodium hydroxide) aqueous solution in a 50 mL glass beaker. The solution was heated to 50 °C and stirred at 600 rotations per minute (rpm) with an overhead mixer for 30 minutes to dissolve the SPI. The solids content of the solution after mixing was 15 wt% soy protein solids.
[0126] A soy protein polyurethane alloy solution was prepared by adding 2.5 g of the SPI solution to 20 g of L3360 from Hauthaway in a 100 mL beaker. The solution was then mixed with an overhead mixer at 150 rpm for 5 minutes. The solution appeared homogenous after mixing. The dry ratio of L3360 solids to SPI solids was 95 to 5 (i.e., about 5 wt% SPI).
[0127] The following five different types of fibers were coated with the soy protein polyurethane alloy solution: (1) DORLASTAN® spandex yarn, (2) Robison-Anton polyester yarn, (3) Robison-Anton nylon yarn, (4) TENCEL™ yam from Shuford Yarns LLC, and (5) silk thread from Clover Needlecraft, Inc.
[0128] Five samples of each fiber were cut and weighed. Then all 25 fiber samples were coated with the soy protein polyurethane alloy solution using the following process. First, the fiber was dipped into the solution, and the solution and fiber were lightly stirred for
10 seconds. After stirring, the fiber was removed from the solution and excess solution on the fiber was removed by sliding the fiber against a solid edge to obtain a substantially even coating. Then the coated fiber was dried in an oven at 75 °C for 10 minutes and cured in a separate oven at 120 °C for additional 10 minutes.
[0129] After drying and curing, the weight of each coated fiber sample was measured and the average coating uptake for each respective fiber type was measured by normalizing the dry weight changes of the individual fibers before and after coating and dividing by the original dry weight of the uncoated fiber. Table 2 below shows the average coating uptake for each of the five fiber types. The average coating uptake is the average coating uptake for the five samples of each respective fiber type.
[0130] The maximum tensile strength and tensile strain (i.e., the percent elongation at break) for samples of the uncoated and coated fibers were also measured using a tensile test method based on ASTM D2256/D2256M with a modified gauge length of 20 mm and testing speed of 100 mm/min. No significant changes in tensile strength or tensile strain were observed between the uncoated and coated fibers.
EXAMPLE 2
[0131] A sample of each of the five coated fibers from Example 1 was dyed with Acid Red 362 dye from Panchmahal Dyestuff Industries using the following process. 500 mg of the dye was added to 150 mL of DI water. The pH of the dye solution was measured and a IN HC1 (hydrochloric acid) solution was added to the dye solution until the pH was between 3 and 4. After a pH of 3 to 4 was achieved, the dye solution was heated to 50 °C on a hot plate. Then each of the five coated fiber samples was placed in the heated dye solution for 20 minutes. After dying for 20 minutes, each fiber was removed from the dye solution and rinsed with warm water.
[0132] Uncoated samples of each of the five fibers were also dyed using the same dye and process. Based on a visual inspection, the coated DORLASTAN® spandex yam exhibited significantly more dye color uptake compared to the uncoated and dyed DORLASTAN® spandex fiber.
EXAMPLE 3
[0133] A soy protein polyurethane alloy solution was prepared by adding 5.2 g of the SPI solution from Example 1 to 20 g of L3360 from Hauthaway in a 100 mL beaker. The solution was then mixed with an overhead mixer at 150 rpm for 5 minutes. The solution appeared homogenous after mixing. The dry ratio of L3360 solids to SPI solids was 90 to 10 (i.e., about 10 wt% SPI).
[0134] Then the following five different types of fibers were coated with the soy protein polyurethane alloy solution: (1) DORLASTAN® spandex yarn, (2) Robison-Anton polyester yarn, (3) Robison-Anton nylon yarn, (4) TENCEL™ yam from Shuford Yarns LLC, and (5) silk thread from Clover Needlecraft, Inc.
[0135] Five samples of each fiber were cut and weighed. Then all 25 fiber samples were coated with the soy protein polyurethane alloy solution using the same process as described in Example 1. The average coating uptake was also measured using the same process as described in Example 1. Table 3 below shows the average coating uptake for each of the five fiber types. The average coating uptake is the average coating uptake for the five samples of each respective fiber type.
[0136] The maximum tensile strength and tensile strain (i.e., the percent elongation at break) for samples of the uncoated and coated fibers were also measured using a tensile test method based on ASTM D2256/D2256M with a modified gauge length of 20 mm and testing speed of 100 mm/min. No significant changes in tensile strength or tensile strain were observed between the uncoated and coated fibers.
EXAMPLE 4
[0137] A sample of each of the five coated fibers from Example 3 was dyed with Acid
Red 362 dye from Panchmahal Dyestuff Industries using the same process as described in Example 2. Based on a visual inspection, the coated DORLASTAN® spandex yarn, the coated Robison-Anton polyester yarn, and the coated Shuford TENCEL™ yam exhibited significantly more dye color uptake compared to the uncoated and dyed samples of the same fibers.
EXAMPLE 5
[0138] A dyed soy protein isolate (SPI) solution was prepared by dissolving 3.75 g SPI (SUPRO® XT 221D-IP; DuPont; available from Solae LLC) in 21.25 mL of a 0.1 mol/L NaOH aqueous solution in a 50 mL glass beaker. 16 mg of Blue-21 reactive dye from Khushi Dye Chem was then added to the 25 g solution. The solution was then heated to 50 °C and stirred at 600 rpm with an overhead mixer for 30 minutes to dissolve the SPI. The solids content of the dyed solution after mixing was about 15 wt% soy protein solids with dye.
[0139] A dyed soy protein polyurethane alloy solution was prepared by adding 2.5 g of the dyed SPI solution to 20 g of L3360 from Hauthaway in a 100 mL beaker. The solution was then mixed with an overhead mixer at 150 rpm for 5 minutes. The solution appeared homogenous after mixing. The dry ratio of L3360 solids to SPI solids was 95 to 5.
[0140] Then five DORLASTAN® spandex yarns were individually dipped into the dyed soy protein polyurethane alloy solution and lightly stirred for 10 seconds. After stirring, the yarns were removed from the dyed solution and excess solution on the yarns was removed by sliding the fiber against a solid edge to obtain a substantially even coating. Then the five coated yarns were dried in an oven at 75 °C for 10 minutes and cured in a separate oven at 120 °C for additional 10 minutes.
[0141] After curing, the coated yams appeared uniformly and evenly dyed. Based on a visual inspection, the coated and dyed yarns exhibited a significant color change compared to uncoated and undyed DORLASTAN® spandex yam.
EXAMPLE 6
[0142] A dyed soy protein polyurethane alloy solution was prepared by adding 5.2 g of the dyed SPI solution from Example 5 to 20 g of L3360 from Hauthaway in a 100 mL beaker. The solution was then mixed with an overhead mixer at 150 rpm for 5 minutes. The solution appeared homogenous after mixing. The dry ratio of L3360 solids to SPI solids was 90 to 10.
[0143] Then five DORLASTAN® spandex yarns were individually dipped into the dyed soy protein polyurethane alloy solution and lightly stirred for 10 seconds. After stirring, the yarns were removed from the dyed solution and excess solution on the yarns was removed by sliding the fiber against a solid edge to obtain a substantially even coating. Then the five coated yarns were dried in an oven at 75 °C for 10 minutes and cured in a separate oven at 120 °C for additional 10 minutes.
[0144] After curing, the coated yams appeared uniformly and evenly dyed. Based on a visual inspection, the coated and dyed yarns exhibited a significant color change compared to uncoated and undyed DORLASTAN® spandex yam.
EXAMPLE 7
[0145] A sample of each of the five coated fibers from Examples 1 and 3 is dyed with Blue-21 reactive dye from Khushi Dye Chem using the following process. 500 mg of the dye is added to 150 mL of DI water. The pH of the dye solution is measured and a IN NaOH solution is added to the dye solution until the pH is between 8 and 9. After a pH of 8 to 9 is achieved, the dye solution is heated to 50 °C on a hot plate. Then each of the five coated fiber samples is placed in the heated dye solution for 20 minutes. After dying for 20 minutes, each fiber is removed from the dye solution and rinsed with warm water.
EXAMPLE 8
[0146] A cellulase solution is prepared by dissolving 4.17 g of cellulase (Native Trichoderma sp. Cellulase; Creative Enzymes®) in 20.85 mL of DI water in a 50 mL glass beaker. The solution is stirred at about 600 rpm with an overhead mixer for 30 minutes to dissolve the cellulase.
[0147] A cellulase polyurethane alloy solution is prepared by adding 2.2 g of the cellulase solution to 20 g of L3360 from Hauthaway in a 100 mL beaker. The solution is then mixed with an overhead mixer at about 150 rpm for 5 minutes.
[0148] The following five different types of fibers are coated with the cellulase polyurethane alloy solution: (1) DORLASTAN® spandex yarn, (2) Robison-Anton polyester yarn, (3) Robison-Anton nylon yarn, (4) TENCEL™ yam from Shuford Yarns LLC, and (5) silk thread from Clover Needlecraft, Inc. The five fiber types are coated with the cellulase polyurethane alloy solution using the following process. First, the fiber is dipped into the solution and the solution and fiber are lightly stirred for 10 seconds. After stirring, the fiber is removed from the solution and excess solution on the fiber is removed by sliding the fiber against a solid edge to obtain a substantially even coating. Then the coated fiber is dried in an oven at 75 °C for 10 minutes and cured in a separate oven at 120 °C for additional 10 minutes.
EXAMPLE 9
[0149] A soy protein isolate (SPI) solution was prepared as described in Example 1. Four coated yarn sample types (Sample Types 9A - 9D) were prepared by coating the yam types listed below in Table 4 with two soy protein polyurethane alloy solutions — a higher viscosity solution with a rheology modifier and a lower viscosity solution without the rheology modifier. Both of the two soy protein polyurethane alloy solutions were prepared by adding 205.88 g of the SPI solution to 794.12 g of L3360 from Hauthaway in a 1000 mL beaker. Each solution was then mixed with an overhead mixer at 150 rpm for 5 minutes. Then, for the first solution, a rheology modifier (RM-4410, from Stahl) was added at 2 wt% of the total solution (20 grams) and a green pigment (PP-39-61 from Permutex) was added at 1 wt% of the total solution. For the second solution, only pink pigment (PP-39-114 from Stahl CAMOTEX®) was added at 1 wt% of the total solution. After adding the rheology modifier and/or pigment, each solution was mixed with an overhead mixer at 300 rpm for 5 minutes. Both solutions appeared homogenous after mixing. The dry ratio of L3360 solids to SPI solids in both solutions was 90 to 10.
[0150] One or more of each of the four yarn types was coated with the soy protein polyurethane alloy solutions as summarized in Table 4 using a single-end CCI SS600 sizing machine available from CCI Tech Inc. The oven temperature of the sizing machine
was set to 49 °C, the speed of the sizing machine was set at the slowest machine setting, and drying time for each coated yam was about six minutes.
[0151] After drying, a uniform coating was visually observed on each coated yarn sample. Further, cross-sectional SEM images of Sample Types 9C and 9C showed the soy protein polyurethane alloy coatings being located on the surface of the yarns, as well as being partially penetrated into the yarn cross-section.
[0152] Also after drying, five yarns of Sample Type C were weighed and the average coating uptake of the yarns was measured by normalizing the dry weight changes of the individual yams before and after coating and dividing by the original dry weight of the uncoated yarn. The average coating uptake for the yarns was 20%.
[0153] Further, after drying, three yams of Sample Type C and three uncoated Shuford TENCEL™ yarns were tested for yam-on-yam abrasion resistance according to ASTM D6611-16 (“Standard Test Method for Wet and Dry Yam-on-Yarn Abrasion Resistance”) with a weight of 50 g and 3 twists in the inter wrapped yarn region. The uncoated yarns had an average abrasion resistance of 75 cycles. The coated yarns of Sample Type C had an average abrasion resistance of 270 cycles.
[0154] Still further, after drying, the maximum tensile strength and tensile strain (i.e., the percent elongation at break) for three yams of Sample Type C and three uncoated Shuford TENCEL™ yarns were measured using a tensile test method based on ASTM D2256/D2256M with a modified gauge length of 20 mm and testing speed of 100 mm/min. The maximum tensile strength and tensile strain were slightly lower for the coated yarns of Sample Type C.
EXAMPLE 10
[0155] A soy protein isolate (SPI) solution was made by dissolving 3.75 g 221D-IP soy protein isolate (SUPRO XT 221D-IP; DuPont; available from Solae LLC) into 21.25 mL of a 0.05 mol/L NaOH aqueous solution in a 50 mL glass beaker. The solution was heated to 50 °C and stirred at 600 rpm with an overhead mixer for 30 minutes. The solids content of the final soy protein solution was 15% soy protein solids.
[0156] A soy protein polyurethane alloy solution was prepared by adding 5.2 g of the SPI solution to 20 g of L3360 from Hauthaway in a 100 mL beaker. The solution was then mixed with an overhead mixer at 150 rpm for 5 minutes. The solution appeared homogenous after mixing. The dry ratio of L3360 solids to SPI solids was 90 to 10 (i.e., about 10 wt% SPI).
[0157] A first cellulase polyurethane alloy solution was prepared by adding 2.43 g of cellulase (Native Trichoderma sp. Cellulase; Creative Enzymes) to 27.82 g of L3360 from Hauthaway in a 40 mL beaker. The solution was mixed at room temperature with an overhead mixer at 500 rpm for 30 minutes. The solution appeared homogenous after mixing. The dry ratio of L3360 solids to cellulase protein solids was 90 to 10 (i.e., about 10 wt% cellulase).
[0158] A second cellulase polyurethane alloy solution was prepared using the same method as the first cellulase polyurethane alloy solution, except 1.51 g of a carbodiimide crosslinker solution (XR-5577 available from Stahl) was added to the 40 mL beaker. The second cellulase polyurethane alloy solution also appeared homogenous after mixing.
[0159] A bovine serum albumin solution was made by dissolving 1.20 g of bovine serum albumin into 10.08 g of water in a 25 mL glass beaker. The solution was then heated to 50 °C and stirred at 600 rpm with an overhead mixer for 30 minutes. The solids content of the final bovine serum albumin solution was 10 wt% protein solids.
[0160] A bovine serum albumin polyurethane alloy solution was prepared by adding the bovine serum albumin solution to 28.8 g of L3360 from Hauthaway in a 50 mL beaker. The solution was then mixed with an overhead mixer at 150 rpm for 5 minutes at room temperature. The solution appeared homogenous after mixing. The dry ratio of L3360 solids to protein solids was 90 to 10 (i.e., about 10 wt% bovine serum albumin).
[0161] A gelatin protein solution was made by dissolving 1.20 g of gelatin from porcine skin into 10.08 g of water in a 25 mL glass beaker. The solution was then heated
to 50 °C and stirred at 600 rpm with an overhead mixer for 30 minutes. The solids content of the final gelatin protein solution was 10 wt% gelatin protein solids.
[0162] A gelatin protein polyurethane alloy solution was prepared by adding the gelatin protein solution to 28.8 g of L3360 from Hauthaway in a 50 mL beaker. The solution was then mixed with an overhead mixer at 150 rpm for 5 minutes at room temperature. The solution appeared homogenous after mixing. The dry ratio of L3360 solids to protein solids was 90 to 10 (i.e., about 10 wt% gelatin).
[0163] Various yarn types were coated with the respective protein polyurethane alloy solutions as shown below in Table 5 to create multiple coated yams according to each sample type (i.e., Sample Types 10A - 10X). Each yarn for each yarn type was coated by dipping the yarn in the respective alloy solution and stirring for the time shown in Table 5. After stirring, each yam was taken out of the alloy solution and excess coating solution was removed by sliding the yarn against a solid edge. After removing excess coating, each yarn was dried in an oven at 75 °C for 10 minutes, and then cured in a separate oven at 120 °C for additional 10 minutes.
[0164] After drying and curing, five yams of each Sample Type 10A - 10X were weighed and the average coating uptake for the yarn types was measured by normalizing the dry weight changes of the individual yarns before and after coating and dividing by the original dry weight of the uncoated yarn. The average coating uptake for each Sample Type 10A - 10X is shown in Table 5. The silk thread in Table 5 is silk thread from Clover Needlecraft, Inc.
EXAMPLE 11
[0165] Six protein polyurethane alloy solutions (Alloy Solutions 11 A - 1 IF) were made according to the following process. First, a soy protein isolate (SPI) solution was made as described in Example 10. Then, Alloy Solutions 11 A - 1 IF were prepared by mixing the amount (in grams) of the SPI solution, the amount (in grams) of polyurethane dispersion,
the additive as shown in Table 6 to respective 100 mL beakers. The alloy solution in each respective beaker was heated to 50 °C and mixed with an overhead mixer at 150 rpm for 5 minutes. All the Alloy Solutions 11 A - 1 IF appeared homogenous after mixing.
Hydran WLS-286BP in Table 6 is an alphatic / polycarbonate type polyurethane dispersion available from DIC Gobal. Impranil DLN W50 in Table 6 is an anionic aliphatic polyester-polyurethane dispersion available from Covestro. SE 2140 waterbased PUD in Table 6 is an aliphatic polyurethane dispersion. L3360 in Table 6 is L3360 from Hauthaway. Stahl RM-4410 is Table 6 is RM-4410 rheology modifier from Stahl.
[0166] Then, for each Alloy Solution 11 A - 1 IF, three 116 centimeter-long Shuford TENCEL™ yarns were individually pulled into a bath of each respective solution and through calipers with a nip gap of 0.076 to remove excess liquid. Each of the 18 coated yarns was then dried in an oven at 75 °C oven for 10 minutes.
[0167] After drying, each yam was weighed and the coating uptake was measured by normalizing the dry weight changes of the individual yarns before and after coating and dividing by the original dry weight of the uncoated yam. The coating uptake for each yarn is shown below in Table 7.
[0168] Also after drying, each yarn was tested for yam-on-yam abrasion resistance according to ASTM D6611-16 (“Standard Test Method for Wet and Dry Yarn-on-Yam Abrasion Resistance”) with a weight of 50 g and 3 twists in the inter wrapped yarn region. The abrasion resistance measured for each yam is also shown in Table 7.
Uncoated Shuford TENCEL™ yarns were also tested for abrasion resistance. The abrasion resistance for the uncoated Shuford TENCEL™ yarns was between 25 and 100 cycles.
EXAMPLE 12
[0169] A first dyed cellulase polyurethane alloy solution was prepared using the following method. First, 2.43 g of cellulase (Native Trichoderma sp. Cellulase; Creative Enzymes) was mixed with 27.82 g of L3360 in a 40 mL beaker. 3 mg of Blue-21 reactive dye available from Chem International. Inc. (Blue-21 dye) was then added to the solution
and the solution was mixed with an overhead mixer at 500 rpm for 30 minutes at room temperature. 10 pL of 10N NaOH was slowly added into the solution while mixing. The solution appeared homogenous after mixing.
[0170] A second dyed cellulase polyurethane alloy solution was prepared using the same method as the first cellulase polyurethane alloy solution, except 1.51 g of a carbodiimide crosslinker solution (XR-5577 available from Stahl) was added to the 40 mL beaker. The second cellulase polyurethane alloy solution also appeared homogenous after mixing.
[0171] A dyed bovine serum albumin polyurethane solution was made using the following process. First, 1.20 g of bovine serum albumin was added into 10.08 g of water in a 25 mL glass beaker. Then, 3 mg of Blue-21 dye was added to the solution and the solution was heated to 50 °C and stirred at 600 rpm with an overhead mixer for 30 minutes. Then, the dyed bovine serum albumin solution was added to 28.8 g of L3360 from Hauthaway in a 50 mL beaker. The solution was then mixed with an overhead mixer at 150 rpm for 5 minutes at room temperature. The solution appeared homogenous after mixing. The dry ratio of L3360 solids to protein solids was 90 to 10 (i.e., about 10 wt% bovine serum albumin).
[0172] A dyed gelatin polyurethane solution was made using the following process. First, 1.20 g of gelatin from porcine skin was added into 10.08 g of water in a 25 mL glass beaker. Then, 3 mg of the Blue-21 dye was added to the solution and the solution was heated to 50 °C and stirred at 600 rpm with an overhead mixer for 30 minutes. Then, the dyed gelatin protein solution was added to 28.8 g of L3360 from Hauthaway in a 50 mL beaker. The solution was then mixed with an overhead mixer at 150 rpm for 5 minutes at room temperature. The solution appeared homogenous after mixing. The dry ratio of L3360 solids to protein solids was 90 to 10 (i.e., about 10 wt% gelatin)
[0173] Five different yarn types were then coated with each respective dyed polyurethane alloy solution. The five different yam types were: (i) DORLASTAN® Spandex yarn, (ii) Robison-Anton polyester yarn, (iii) Robison-Anton nylon yam, (iv) Shuford TENCEL™ yarn, and (v) silk thread from Clover Needlecraft, Inc.
[0174] Each yam was coated in each respective solution using the following process. Each yam was dipped into the respective alloy solution and stirred for 10 minutes. After stirring, each yam was taken out of the alloy solution and excess coating solution was removed by sliding the yam against a solid edge. After removing excess coating, each
yarn was dried in an oven at 75 °C for 10 minutes, and then cured in a separate oven at 120 °C for additional 10 minutes.
[0175] After drying and curing, each yarn coated with each respective dyed polyurethane alloy solution appeared uniformly and evenly dyed.
EXAMPLE 13
[0176] Coated yam types from Examples 10 and 11 were dyed with the dyes as shown below in Table 8. Acid Blue 158 in Table 8 is Acid Blue 158 dye from Panchmahal Dyestuff Industries. Reactive Black 5 in Table 8 is Reactive Black 5 dye from Dye-Chem International. Acid Red 362 in Table 8 is Acid Red 362 dye from Panchmahal Dyestuff Industries. Reactive Blue 11 in Table 8 is Reactive Blue 11 dye from Dye-Chem International. Reactive Blue 21 in Table 8 is Reactive Blue 21 dye from Dye-Chem International.
[0177] Coated yams dyed with Acid Blue 158 were dyed according to the following process. 650 mg of Acid Blue 158 dye was added to 200 mL of DI water in a beaker. The pH of the solution was measured and drops of IN HC1 were added to the solution until the pH read between 3 and 4. The beaker with the solution was then placed on a hot plate and heated to 60 °C. Then the yarns were placed in the heated solution and allowed to soak for 1 hour. After soaking, the yarns were removed from the beaker and washed with warm water. Uncoated yams were also dyed using the same process.
[0178] The dyed yarns of Type 10B visually showed more dye color uptake when compared to the uncoated yams after dying.
[0179] Coated yams dyed with Reactive Black 5 were dyed according to the following process. 650 mg of Reactive Black 5 dye was added to 200 mL of DI water in a beaker. The pH of the solution was measured and drops of IN NaOH were added to the solution until the pH read between 9 and 10. The beaker with the solution was then placed on a hot plate and heated to 60 °C. Then the yarns were placed in the heated solution and allowed to soak for 1 hour. After soaking, the yarns were removed from the beaker and washed with warm water. Uncoated yarns were also dyed using the same process.
[0180] The dyed yams of Type 10D visually showed more dye color uptake when compared to the uncoated yams after dying.
[0181] Coated yams dyed with Acid Red 362 were dyed according to the following process. 500 mg of Acid Red 362 dye was added to 150 mL of DI water in a beaker. The pH of the solution was measured and drops of IN HC1 were added to the solution until the pH read between 3 and 4. The beaker with the solution was then placed on a hot plate and heated to 60 °C for Yam Types 10F and 10H, and 50 °C for Yarn Types 10P, 10R, 10T and 10U, TENCEL™ yarn coated with Solution 1 IE, and TENCEL™ yarn coated with Solution 1 IF. The yams were placed in the heated solution and allowed to soak. Yarn Types 10F and 10H were allowed to soak for 16 hours, while Yarn Types 10P, 10R, 10T and 10U, TENCEL™ yarn coated with Solution 1 IE, and TENCEL™ yarn coated with Solution 1 IF were allowed to soak for 30 minutes. After soaking, the yams were
removed from the beaker and washed with warm water. Uncoated yams were also dyed using the same processes.
[0182] All the coated yarns dyed with Acid Red 362 dye visually showed more dye color uptake when compared to corresponding uncoated yams after dying.
[0183] Coated yams dyed with Reactive Blue 11 were dyed according to the following process. 650 mg of Reactive Blue 11 dye was added to 200 mL of DI water in a beaker. The pH of the solution was measured and drops of IN NaOH were added to the solution until the pH read between 9 and 10. The beaker with the solution was then placed on a hot plate and heated to 60 °C. Then the yarns were placed in the heated solution and allowed to soak for 16 hours. After soaking, the yams were removed from the beaker and washed with warm water. Uncoated yarns were also dyed using the same process.
[0184] The dyed yarns of Types 10H and 10M visually showed more dye color uptake when compared to corresponding uncoated yarns after dying.
[0185] Coated yams dyed with Reactive Blue 21 were dyed according to the following process. 650 mg of Reactive Blue 21 dye was added to 200 mL of DI water in a beaker. The pH of the solution was measured and drops of IN NaOH were added to the solution until the pH read between 9 and 10. The beaker with the solution was then placed on a hot plate and heated to 50 °C. Then the yarns were placed in the heated solution and allowed to soak for 1 hour. After soaking, the yarns were removed from the beaker and washed with warm water. Uncoated yarns were also dyed using the same process.
[0186] All the coated yarns dyed with Reactive Blue 21 visually showed more dye color uptake when compared to corresponding uncoated yams after dying.
[0187] While various embodiments have been described herein, they have been presented by way of example, and not limitation. It should be apparent that adaptations and modifications are intended to be within the meaning and range of equivalents of the disclosed embodiments, based on the teaching and guidance presented herein. It therefore will be apparent to one skilled in the art that various changes in form and detail can be made to the embodiments disclosed herein without departing from the spirit and scope of the present disclosure. The elements of the embodiments presented herein are not necessarily mutually exclusive, but can be interchanged to meet various situations as would be appreciated by one of skill in the art.
[0188] Embodiments of the present disclosure are described in detail herein with reference to embodiments thereof as illustrated in the accompanying drawings, in which
like reference numerals are used to indicate identical or functionally similar elements. References to “one embodiment,” “an embodiment,” “some embodiments,” “in certain embodiments,” etc., indicate that the embodiment described can include a particular feature, structure, or characteristic, but every embodiment can not necessarily include the particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is submitted that it is within the knowledge of one skilled in the art to affect such feature, structure, or characteristic in connection with other embodiments whether or not explicitly described.
[0189] The examples are illustrative, but not limiting, of the present disclosure. Other suitable modifications and adaptations of the variety of conditions and parameters normally encountered in the field, and which would be apparent to those skilled in the art, are within the spirit and scope of the disclosure.
[0190] It is to be understood that the phraseology or terminology used herein is for the purpose of description and not of limitation. The breadth and scope of the present disclosure should not be limited by any of the above-described exemplary embodiments, but should be defined in accordance with the following claims and their equivalents.
SEQUENCES
SEQ ID NO: 1 : Collagen Fragment
DVKSGVAVGGLAGYPGPAGPPGPPGPPGTSGHPGSPGSPGYQGPPGEPGQAG
PSGPPGPPGAIGPSGPAGKDGESGRPGRPGERGLPGPPGIKGPAGIPGFPGMKG
HRGFDGRNGEKGETGAPGLKGENGLPGENGAPGPMGPRGAPGERGRPGLPG
AAGARGNDGARGSDGQPGPPGPPGTAGFPGSPGAKGEVGPAGSPGSNGAPG QRGEPGPQGHAGAQGPPGPPGINGSPGGKGEMGPAGIPGAPGLMGARGPPGP AGANGAPGLRGGAGEPGKNGAKGEPGPRGERGEAGIPGVPGAKGEDGKDGS
PGEPGANGLPGAAGERGAPGFRGPAGPNGIPGEKGPAGERGAPGPAGPRGAA
GEPGRDGVPGGPGMRGMPGSPGGPGSDGKPGPPGSQGESGRPGPPGPSGPRG QPGVMGFPGPKGNDGAPGKNGERGGPGGPGPQGPPGKNGETGPQGPPGPTG PGGDKGDTGPPGPQGLQGLPGTGGPPGENGKPGEPGPKGDAGAPGAPGGKG DAGAPGERGPPAIAGIGGEKAGGFAPYYG
Claims
WHAT IS CLAIMED IS: A coated fiber, comprising: a core fiber; and a coating disposed over the core fiber, the coating comprising a protein dissolved within a polyurethane. The coated fiber of claim 1, wherein the protein is a soy protein. The coated fiber of claim 2, wherein the soy protein is soy protein isolate. The coated fiber of any one of claims 1-3, further comprising a dye. The coated fiber of claim 4, wherein the coating comprises the dye. The coated fiber of any one of claims 1-5, wherein the coated fiber has a coating uptake of greater than or equal to about 10%. The coated fiber of any one of claims 1-5, wherein the coated fiber has a coating uptake ranging from about 10% to about 100%. The coated fiber of any one of claims 1-7, wherein the coating has a thickness of greater than or equal to about 100 nanometers. The coated fiber of any one of claims 1-7, wherein the coating has a thickness ranging from about 100 nanometers to about 1 millimeter. The coated fiber of any one of claims 1-9, wherein the coating has a thickness greater than or equal to 1% of an effective diameter of the core fiber. The coated fiber of any one of claims 1-10, wherein the coating comprises about 5 wt% to about 50 wt% of the protein and about 50 wt% to about 95 wt% of the polyurethane. The coated fiber of any one of claims 1 or 4-11, wherein the protein is an enzyme.
The coated fiber of any one of claims 1 or 4-11, wherein the protein is selected from the group consisting of soy protein, collagen, gelatin, bovine serum albumin, pea protein, egg white albumin, casein protein, peanut protein, edestin protein, whey protein, karanja protein, hemp protein, an enzyme, and cellulase. A method of making a coated fiber, the method comprising: coating a core fiber with a coating comprising a protein dissolved within a polyurethane. The method of claim 14, wherein coating the core fiber comprises a dip coating process. The method of claim 14 or claim 15, further comprising dying the coating. The method of claim 16, wherein the coating is dyed after the coating is coated on the core fiber. The method of claim 16, wherein the coating is dyed before the coating is coated on the core fiber. A material, comprising: a plurality of the coated fibers according to any one of claims 1-13, wherein a first coated fiber is in contact with a second coated fiber, and wherein the first and second coated fibers can slide over each other. The material of claim 19, further comprising a fiber not coated with a protein dissolved within a polyurethane, wherein the first coated fiber is in contact with the fiber not coated with a protein dissolved within a polyurethane, and wherein the first coated fiber and the fiber not coated with a protein dissolved within a polyurethane can slide over each other. The material of claim 19, wherein the amount of the coating disposed on the coated fibers within the material is uniform through a cross-sectional thickness of the material such that all the coated fibers within the material have a coating uptake that is substantially the same.
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