WO2025019796A1

WO2025019796A1 - Bio-based leather

Info

Publication number: WO2025019796A1
Application number: PCT/US2024/038796
Authority: WO
Inventors: Neel Elsherif
Original assignee: Melasworld Inc
Current assignee: Melasworld Inc
Priority date: 2023-07-19
Filing date: 2024-07-19
Publication date: 2025-01-23
Anticipated expiration: 2026-01-19

Abstract

In one aspect, the invention relates to bio-based leathers that do not contain polyurethane (PU) or polyvinyl chloride (PVP) or dimethylformamide (DMF). Also disclosed are methods of making bio-based leathers.

Description

BIO-BASED LEATHER

BACKGROUND

[0001] Turning animal skin into leather requires a massive amount of energy and chemicals and also expels large amounts of toxic waste into the environment.

[0002] Vegan leather is artificial, synthetic, or “faux” leather made from agricultural waste products and sustainable biomaterials. It can also be made from polymers like polyurethane and other recyclable materials. Vegan leather is an alternative to animal leather and is made without using any animal products. Vegan leather is environmentally friendly, biodegradable, and animal -cruelty -free.

[0003] The majority of vegan leather options on the market comprise from 25-60% polyurethane (PU) or polyvinyl chloride (PVC). The inclusion of these oil-based products does not solve the carbon emissions challenges and can still have a negative impact on the environment. Furthermore, people can develop an allergy to faux leather containing PU or PVC.

[0004] What is needed are alternative vegan leathers that do not comprise PU or PVC. Also needed are methods of making vegan leathers that do not comprise PU or PVC.

BRIEF SUMMARY

[0005] Described herein are bio-based leathers as well as methods for making bio-based leathers. For example, disclosed are bio-based leathers that do not comprise polyurethane (PU) or polyvinyl chloride (PVC)

[0006] Disclosed herein are bio-based leathers comprising (a) a bio-polymer mixture comprising (i) about 25% to about 60% of a plant-based composition comprising vegetal material, and (ii) about 40% to about 75% of a curative pre-polymer mixture; and (b) a fiber cloth.

[0007] Disclosed herein are methods of making a bio-based leather comprising: (a) preparing a plant-based composition, wherein the plant-based composition comprises vegetal material in powder form; (b) preparing a curative pre-polymer mixture, wherein the curative pre-polymer mixture comprises a solvent and a polymer; (c) combining the plant-based composition and the curative pre-polymer mixture to form a bio-polymer mixture; (d) applying the bio-polymer mixture to a fiber cloth; and (e) applying heat to the composition of step (d), thereby forming a bio-based leather. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several aspects of the disclosed method and compositions and together with the description, serve to explain the principles of the disclosed method and compositions.

[0009] FIG. l is a flow chart of an exemplary method of manufacturing a bio-based leather.

DETAILED DESCRIPTION

[0010] The disclosed method and compositions may be understood more readily by reference to the following detailed description of particular aspects and the Examples included therein and to the Figures and their previous and following description.

[0011] It is to be understood that the disclosed method and compositions are not limited to specific synthetic methods, specific analytical techniques, or to particular reagents unless otherwise specified, and. as such, may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting.

A. Definitions

[0012] The terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting.

[0013] Throughout the description and claims of this specification, the word “comprise” and variations of the word, such as “comprising” and “comprises,” means “including but not limited to,” and is not intended to exclude, for example, other additives, components, integers or steps. In particular, in methods stated as comprising one or more steps or operations it is specifically contemplated that each step comprises what is listed (unless that step includes a limiting term such as “consisting of’), meaning that each step is not intended to exclude, for example, other additives, components, integers or steps that are not listed in the step.

[0014] As used in the specification and the appended claims, the singular forms “a,” “an” and “the” can include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a compound” includes mixtures of compounds, reference to “a pharmaceutical carrier” includes mixtures of two or more such carriers, and the like.

[0015] The word “or” as used herein means any one member of a particular list and also includes any combination of members of that list.

[0016] Ranges may be expressed herein as from “about” one particular value, and/or to “about"’ another particular value. The term "about" is used herein to mean approximately, in the region of, roughly, or around. When the term "about" is used in conjunction with a numerical range, it modifies that range by extending the boundaries above and below the numerical values set forth. In general, the term “about” is used herein to modify a numerical value above and below the stated value by a variance of 20%. When such a range is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0017] By “flexometries” is meant herein the flexibility of a material. Flexometries can be measured with a flexometer. The flexometer can check how the leather surface behaves when continuously wrinkled. The Bally Flexometer is by far the most widely used instrument to measure the flexibility of a material. It can assess the flexing endurance and can count the number of movement repetitions before the leather surface starts to become brittle and form cracks.

[0018] By "room temperature" or its abbreviation, "rt" is meant herein that the reactions or processes are performed without heating or cooling. Generally, by room temperature may be understood as a temperature between about 15 °C and about 30 °C, or more particularly between about 20 °C and about 25 °C.

[0019] Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of skill in the art to which the disclosed method and compositions belong. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present method and compositions, the particularly useful methods, devices, and materials are as described. Publications cited herein and the material for which they are cited are hereby specifically incorporated by reference. Nothing herein is to be construed as an admission that the present invention is not entitled to antedate such disclosure by virtue of prior invention. No admission is made that any reference constitutes prior art. The discussion of references states what their authors assert, and applicants reserve the right to challenge the accuracy and pertinency of the cited documents. It will be clearly understood that, although a number of publications are referred to herein, such reference does not constitute an admission that any of these documents forms part of the common general knowledge in the art. B. Bio-Based Leather

[0020] Non-limiting examples of the compositions of the bio-based leather are provided herein.

[0021] Disclosed herein are bio-based leathers comprising (a) a bio-polymer mixture comprising (i) about 25% to about 60% of a plant-based composition comprising vegetal material, and (ii) about 40% to about 75% of a curative pre-polymer mixture; and (b) a fiber cloth.

[0022] In some aspects, the bio-based leather does not comprise polyurethane (PU) or polyvinyl chloride (PVC). In some aspects, the bio-based leather is 100% plant-based material.

1. Bio-Polymer Mixture

[0023] As used herein, the term ‘'bio-polymer mixture” refers to a mixture of a plant-based composition and a curative pre-polymer mixture.

In some aspects, bio-polymer mixture comprises about 25% (vol/vol) to about 60% (vol/vol) of a plant-based composition. In some aspects, bio-polymer mixture comprises about 30% (vol/vol) to about 60% (vol/vol) of a plant-based composition. In some aspects, bio-polymer mixture comprises about 35% (vol/vol) to about 60% (vol/vol) of a plant-based composition. In some aspects, bio-polymer mixture comprises about 40% (vol/vol) to about 60% (vol/vol) of a plant-based composition. In some aspects, bio-polymer mixture comprises about 45% to about 60% (vol/vol) of a plant-based composition. In some aspects, bio-polymer mixture comprises about 50% (vol/vol) to about 60% (vol/vol) of a plant-based composition. In some aspects, bio-polymer mixture comprises about 55% (vol/vol) to about 60% (vol/vol) of a plant-based composition.

[0024] In some aspects, bio-polymer mixture comprises about 25% (vol/vol) to about 55% (vol/vol) of a plant-based composition. In some aspects, bio-polymer mixture comprises about 25% (vol/vol) to about 50% (vol/vol) of a plant-based composition. In some aspects, bio-polymer mixture comprises about 25% (vol/vol) to about 45% (vol/vol) of a plant-based composition. In some aspects, bio-polymer mixture comprises about 25% (vol/vol) to about 40% (vol/vol) of a plant-based composition. In some aspects, bio-polymer mixture comprises about 25% (vol/vol) to about 35% (vol/vol) of a plant-based composition. In some aspects, bio-polymer mixture comprises about 25% (vol/vol) to about 30% (vol/vol) of a plant-based composition.

[0025] In some aspects, bio-polymer mixture comprises about 30% (vol/vol) to about 55% (vol/vol) of a plant-based composition. In some aspects, bio-polymer mixture comprises about 35% (vol/vol) to about 50% (vol/vol) of a plant-based composition. In some aspects, bio-polymer mixture comprises about 40% (vol/vol) to about 45% (vol/vol) of a plant-based composition.

[0026] In some aspects, bio-polymer mixture comprises about (vol/vol) 40% to about (vol/vol) 75% of a curative pre-polymer mixture. In some aspects, bio-polymer mixture comprises about 45% (vol/vol) to about 75% (vol/vol) of a curative pre-polymer mixture. In some aspects, bio-polymer mixture comprises about 50% (vol/vol) to about 75% (vol/vol) of a curative pre-polymer mixture. In some aspects, bio-polymer mixture comprises about 55% (vol/vol) to about 75% (vol/vol) of a curative pre-polymer mixture. In some aspects, biopolymer mixture comprises about 60% (vol/vol) to about 75% (vol/vol) of a curative prepolymer mixture. In some aspects, bio-polymer mixture comprises about 65% (vol/vol) to about 75% (vol/vol) of a curative pre-polymer mixture. In some aspects, bio-polymer mixture comprises about 70% (vol/vol) to about 75% (vol/vol) of a curative pre-polymer mixture.

[0027] In some aspects, bio-polymer mixture comprises about 40% (vol/vol) to about 70% (vol/vol) of a curative pre-polymer mixture. In some aspects, bio-polymer mixture comprises about 40% (vol/vol) to about 65% (vol/vol) of a curative pre-polymer mixture. In some aspects, bio-polymer mixture comprises about 40% (vol/vol) to about 60% (vol/vol) of a curative pre-polymer mixture. In some aspects, bio-polymer mixture comprises about 40% (vol/vol) to about 55% (vol/vol) of a curative pre-polymer mixture. In some aspects, biopolymer mixture comprises about 40% (vol/vol) to about 50% (vol/vol) of a curative prepolymer mixture. In some aspects, bio-polymer mixture comprises about 40% (vol/vol) to about 45% (vol/vol) of a curative pre-polymer mixture.

[0028] In some aspects, bio-polymer mixture comprises about 45% (vol/vol) to about 70% (vol/vol) of a curative pre-polymer mixture. In some aspects, bio-polymer mixture comprises about 50% (vol/vol) to about 65% (vol/vol) of a curative pre-polymer mixture. In some aspects, bio-polymer mixture comprises about 55% (vol/vol) to about 60% (vol/vol) of a curative pre-polymer mixture.

[0029] In some aspects, bio-polymer mixture comprises about 30% (vol/vol) to about 40% (vol/vol) of a plant-based composition. In some aspects, bio-polymer mixture comprises about 35% (vol/vol) of a plant-based composition.

[0030] In some aspects, bio-polymer mixture has a viscosity of about 1500 to about 3500 centipoise (cps). In some aspects, bio-polymer mixture has a viscosity of about 2000 to about 3000 cps. In some aspects, bio-polymer mixture has a viscosity of about 2000 cps. about 2500 cps or about 3000 cps. i. Plant-Based Composition

[0031] As used herein, “plant-based composition" is meant a composition that is comprised primarily of dried vegetal material. In some aspects the plant-based composition is a dried vegetal material that has been ground into a flour. An example of a plant-based composition can be found in US 2009/0301347.

[0032] In some aspects, the plant-based composition has a particle size of about 10 pm to about 1000 pm. In some aspects, the plant-based composition has a particle size of about 10 pm to about 840 pm. In some aspects, the plant-based composition has a particle size of about 20 pm to about 1000 pm. In some aspects, the plant-based composition has a particle size of about 75 pm to about 150 pm. In some aspects, the plant-based composition has a moisture level of between about 12% and about 18%.

[0033] In some aspects, the plant-based composition is about 100% plant-based material. In some aspects, the plant-based composition is 100% plant-based material.

[0034] In some aspects, the vegetal material is apple, apricot, avocado, orange, Amazon grape, araza, alligator apple, ambarella, African cucumber, African medlar, agave plant, aizen fruit, aprium. banana, beach plum, black apple, burdekin plum, blood orange, babaco, bael, barbadine, bilimbi, black sapote, bottle gourd, Burmese grape, bignay, balsam apple, batuan fruit, blood lime, Brazilian guava, cantaloupe, calabash, calamansi, calamondins, canistel, cape gooseberry, cashew apple, chayote fruit, citrofortunella, clementines, coco plum, cucumber, damson, date plum, davidson's plum, dekopon, desert lime, dragon fruit, eastern hawthorn, elephant apple, emu apple, fairchild tangerine, false mastic, feijoa, gac fruit, galia melon, genip, golden apple, goumi fruit, governor’s plum, grapefruit, grapes, grapple, greengage, ground plum, guarana, guava berry, hardy-kiwi, honeydew, honeysuckle, homed melon, illawarra plum, imbe fruit, Indian jujube, Indian prune, jabotacaba, jambul fruit, Japanese persimmon, jocote, jujube, kabosu fruit, kaffir lime, kahikatea, kakadu plum, karonda, kei apple, kiwi, kumquat, kundong, kwai muk, lady apple, langsat, lemato, lemon aspen, lemons, limeberry, limequat, loquat, lucuma, lychee, malay apple, mamey sapote, mammee apple, mamoncillo, mandarin, mangaba. ma-praang, marula, mayapple, melonpear, miracle fruit, muscadine, naartjie, nance, naranjilla. nectacotum, nectarines, nonda plum, nungu, orangelo, oranges, Oregon grape, oroblanco, ortanique, papaya, passion fruit, peach, peach palm, pears, pequi, persian lime, persimmon, phalsa, physalis fruit, pigeon plum, pine apple, plum, plumcot, pluot, pomato, pulasan, pummelo, rangpur. red mombin. rose apple, sapodilla, star apple, star fruit, strawberry guava, sugar apple, sweet orange, tangelo, tangor. tomato, ugli, velvet apple, watermelon, wax jambu, white sapote, yuzu or a mixture thereof. [0035] In some aspects, the vegetal material is apple, grape, cactus, mango, orange, tomato, pineapple or a mixture thereof. In some aspects, the vegetal material is apple. ii. Curative Pre-Polymer Mix

[0036] As used herein, “curative pre-polymer mixture” is meant an elastomeric product comprising an epoxidized polymer and a polyfunctional carboxylic acid, such as the mixtures found in USPN 10.882,951.

[0037] In some aspects, the curative pre-polymer mixture comprises an epoxidized polymer. In some aspects, the epoxidized polymer is epoxidized natural rubber (ENR) or epoxidized vegetable oil. In some aspects, the epoxidized polymer is ENR. In some aspects, the epoxidized polymer is ENR25. In some aspects, the ENR is Epoxyprene® (Sanyo Corp.). In some aspects, the epoxidized vegetable oil is epoxidized soybean oil, epoxidized canola oil or epoxidized olive oil.

[0038] In some aspects, the epoxidized polymer comprises about 25% epoxidation. In some aspects, the epoxidized polymer comprises about 50% epoxidation.

[0039] In some aspects, the curative pre-polymer mixture comprises about 5% (vol/vol) to about 25% (vol/vol) of an epoxidized polymer. In some aspects, the curative pre-polymer mixture comprises about 5% (vol/vol) to about 10% (vol/vol) of an epoxidized polymer. In some aspects, the curative pre-polymer mixture comprises about 5% (vol/vol) to about 15% (vol/vol) of an epoxidized polymer. In some aspects, the curative pre-polymer mixture comprises about 5% (vol/vol) of an epoxidized polymer. In some aspects, the curative prepolymer mixture comprises about 10% (vol/vol) of an epoxidized polymer. In some aspects, the curative pre-polymer mixture comprises about 15% (vol/vol) of an epoxidized polymer. In some aspects, the curative pre-polymer mixture comprises about 20% (vol/vol) of an epoxidized polymer. In some aspects, the curative pre-polymer mixture comprises about 25% (vol/vol) of an epoxidized polymer.

[0040] In some aspects, the poly functional carboxylic acid is citric acid, tartaric acid, succinic acid, malic acid, maleic acid, fumaric acid and/or polylactic acid.

[0041] In some aspects, the polyfunctional carboxylic acid is citric acid. In some aspects, the polyfunctional carboxylic acid is citric acid powder.

[0042] In some aspects, the curative pre-polymer mixture comprises about 10% (vol/vol) to about 40% (vol/vol) of a polyfunctional carboxylic acid. In some aspects, the curative prepolymer mixture comprises about 15% (vol/vol) to about 25% (vol/vol) of a polyfunctional carboxylic acid. In some aspects, the curative pre-polymer mixture comprises about 10% (vol/vol) of a poly functional carboxylic acid. In some aspects, the curative pre-polymer mixture comprises about 15% (vol/vol) of a polyfunctional carboxylic acid. In some aspects, the curative pre-polymer mixture comprises about 20% (vol/vol) of a polyfunctional carboxylic acid. In some aspects, the curative pre-polymer mixture compnses about 25% (vol/vol) of a polyfunctional carboxylic acid. In some aspects, the curative pre-polymer mixture comprises about 30% (vol/vol) of a polyfunctional carboxylic acid. In some aspects, the curative pre-polymer mixture comprises about 35% (vol/vol) of a polyfunctional carboxylic acid. In some aspects, the curative pre-polymer mixture comprises about 40% (vol/vol) of a polyfunctional carboxylic acid.

[0043] In some aspects, the poly functional carboxylic acid is PLA (polylactic acid). PLA is typically made from the sugars in com starch, cassava or sugarcane. It is biodegradable, carbon-neutral and edible. To transform com into plastic, com kernels are immersed in sulfur dioxide and hot water, where its components break down into starch, protein, and fiber. The kernels are then ground and the com oil is separated from the starch. The starch is comprised of long chains of carbon molecules, similar to the carbon chains in plastic from fossil fuels. Some citric acids are mixed in to form a long-chain polymer (a large molecule consisting of repeating smaller units) that is the building block for plastic. PLA can look and behave like polyethylene (used in plastic films, packing and bottles), polystyrene (Styrofoam and plastic cutlery) or polypropylene (packaging, auto parts, textiles). In some aspects, the PLA is about 15 pm to about 25 pm. In some aspects, the PLA is about 20 pm thick and may have a density of about 1.24 g/cm³, biobased, biodegradable and compostable, with high transparency and gloss, high mechanical resistance.

[0044] In some aspects, the curative pre-polymer mixture further comprises an alcohol, such as, but not limited to, ethanol, methanol, pentanol, propanol, butanol, hexanol, or mixtures thereof.

[0045] In some aspects, the curative pre-polymer mixture comprises about 15% (vol/vol) to about 50% (vol/vol) of an alcohol. In some aspects, the curative pre-polymer mixture comprises about 30% (vol/vol) to about 40% (vol/vol) of an alcohol. In some aspects, the curative pre-polymer mixture comprises about 15% (vol/vol) of an alcohol. In some aspects, the curative pre-polymer mixture comprises about 20% (vol/vol) of an alcohol. In some aspects, the curative pre-polymer mixture comprises about 25% (vol/vol) of an alcohol. In some aspects, the curative pre-polymer mixture comprises about 30% (vol/vol) of an alcohol. In some aspects, the curative pre-polymer mixture comprises about 35% (vol/vol) of an alcohol. In some aspects, the curative pre-polymer mixture comprises about 40% (vol/vol) of an alcohol. In some aspects, the curative pre-polymer mixture comprises about 45% (vol/vol) of an alcohol. In some aspects, the curative pre-polymer mixture comprises about 50% (vol/vol) of an alcohol.

[0046] In some aspects, the curative pre-polymer mixture further comprises an oil, such as, but not limited to, soybean oil, palm oil, coconut oil, rapeseed oil, sunflower oil, olive oil, com oil, avocado oil, safflower oil, peanut oil, canola oil, sunflower oil, flaxseed oil, or a mixture thereof.

[0047] In some aspects, the curative pre-polymer mixture comprises about 25% (vol/vol) to about 75% (vol/vol) of an oil. In some aspects, the curative pre-polymer mixture comprises about 35% (vol/vol) to about 50% (vol/vol) of an oil. In some aspects, the curative prepolymer mixture comprises about 25% (vol/vol) of an oil. In some aspects, the curative prepolymer mixture comprises about 30% (vol/vol) of an oil. In some aspects, the curative prepolymer mixture comprises about 35% (vol/vol) of an oil. In some aspects, the curative prepolymer mixture comprises about 40% (vol/vol) of an oil. In some aspects, the curative prepolymer mixture comprises about 45% (vol/vol) of an oil. In some aspects, the curative prepolymer mixture comprises about 50% (vol/vol) of an oil. In some aspects, the curative prepolymer mixture comprises about 55% (vol/vol) of an oil. In some aspects, the curative prepolymer mixture comprises about 60% (vol/vol) of an oil. In some aspects, the curative prepolymer mixture comprises about 65% (vol/vol) of an oil. In some aspects, the curative prepolymer mixture comprises about 70% (vol/vol) of an oil. In some aspects, the curative prepolymer mixture comprises about 75% (vol/vol) of an oil.

2. Fiber Cloth

[0048] As used herein, “fiber cloth” refers to a cloth made from natural materials or synthetic materials. In some aspects, the fiber cloth does not comprise any animal based fibers. Examples of natural fiber cloths include, but are not limited to cotton, bamboo, linen (made from flax), hemp and jute. An example of synthetic fiber cloth includes, but is not limited to, a microfiber cloth.

[0049] In some aspects, the fiber cloth is cotton, bamboo, jute or microfiber.

3. Characteristics of Bio-Based Leather

[0050] In some aspects, the bio-based leather has a weight of about 250 g/m² to about 570 g/m² The weight of the bio-based leather can be measured by any method known in the art. For example, the bio-based leather can be cut into a circle having a known area and then weighed using a digital scale.

[0051] In some aspects, the bio-based leather has a thickness of about 0.5 mm to about 1.2 mm. The thickness of the bio-based leather can be measured by any method known in the art, including, but not limited to a Fujiyuan 1 Leather Craft Tool Thickness Gauge Tester or a leather caliper such as Tandy Leather Wing Divider 3607-00.

[0052] In some aspects, the bio-based leather has a tensile strength along the grain of greater than about 280, greater than about 300, greater than about 350, or greater than about 500 N/5cm. In some aspects, the bio-based leather has a tensile strength across the grain of greater than about 15, greater than about 80. greater than about 120, greater than about 500, greater than about 600 or greater than about 650 N/5cm. the tensile strength of the bio-based leather can be measured by any method known in the art, such as on a INSTRON 441 1 Tensile Compression Pull Tester Machine.

[0053] In some aspects, the bio-based leather has a maximum (max) elongation along the grain of greater than about 13%. greater than about 15%, greater than about 20%, greater than about 30% or greater than about 100%. In some aspects, the bio-based leather has a maximum (max) elongation across the grain of greater than about 13%, greater than about 20%, greater than about 30%, greater than about 100%, greater than about 110% or greater than about 250%. The maximum elongation of the bio-based leather can be measured by any method known in the art, such as on an INSTRON 4411 Tensile Compression Pull Tester Machine.

[0054] In some aspects, the bio-based leather has a tear strength along the grain of greater than 10N, greater than about 12N, greater than about 15N, or greater than about 25N. In some aspects, the bio-based leather has a tear strength across the grain of greater than about 7N, greater than about 10N, greater than about 12N, greater than about 15N, greater than about 20N, or greater than about 3 ON. The tear strength of the bio-based leather can be measured by any method known in the art including, for example, using a CMC Kuhnke Pop and Tear Tester.

[0055] In some aspects, the bio-based leather has an adhesion along the grain of greater than about 7 N/5cm, greater than about 15 N/5cm, greater than about 20 N/5cm, greater than about 25 N/5cm, greater than about 30 N/5cm, or greater than about 35 N/5cm. In some aspects, the bio-based leather has an adhesion across the grain of greater than about 3 N/5cm, greater than about 20 N/5cm, greater than about 25 N/5cm. greater than about 30 N/5cm, or greater than about 35 N/5cm. The adhesion of the bio-based leather can be measured by any method known in the art, including, for example, by using a cylinder probe to measure the force needed to pull the probe off the surface of the sample (the higher the force, the more adhesive the product). [0056] In some aspects, the bio-based leather has flexometries of greater than about 100,000 cycles, greater than about 120,000 cycles, or greater than about 150,000 cycles. The flexometries of the bio-based leather can be measured by any method known in the art, including but not limited to, using a flexometer, such as the EKT-2002GF by Ektron.

[0057] In some aspects, the bio-based leather has abrasion resistance of greater than about 6,400 cycles, greater than about 51,200 cycles, greater than about 60,000 cycles, or greater than about 100,000 cycles. The abrasion resistance of the bio-based leather can be measured by any method known in the art, including, for example, an abrasion resistance scrub tester. [0058] In some aspects, the bio-based leather has a color fastness of 4/5 or 5/5. The color fastness of the bio-based leather can be measured by any method known in the art, such as, for example, a low temperature launder-odometer, a weather-o-meter, or a launder-o-meter. [0059] In some aspects, the bio-based leather comprises a microencapsulated fragrance. Microencapsulation is a technology that encapsulates active and volatile substances to form nano- or micro-scale capsules. It may be able to protect the core materials from the surrounding environment and provide some new applications and release characteristic. The fragrances useful in practicing the invention include any material which can impart a desirable odor or enhance an existing smell or odor to a substrate such as, for example air fresheners, laundry' detergents, fabric softeners, deodorants, lotions, and other household items. Such fragrances generally contain at least one essential oil. Non-limiting examples of fragrances include essential oils, such as, for example, d-limonene, eugenol, orange, lemon, eucalyptol (cineol), clove oil and the like. Also useful in practicing the invention are commercially available fragrances w hich include materials, such as, for example, Autre Melange, or MixTex 1 from Givaudan-Roure, France and the like.

[0060] Examples of microencapsulated fragrances, include, but are not limited to microencapsulated fragrances available from Celessence Technologies Ltd.

[0061] In some aspects, the fragrances are applied to the fiber cloth prior to applying the bio-polymer mixture to the fiber cloth.

C. Methods For Making a Bio-Based Leather

[0062] Disclosed herein are methods of making a bio-based leather comprising: (a) preparing a plant-based composition, wherein the plant-based composition comprises vegetal material in powder form; (b) preparing a curative pre-polymer mixture, wherein the curative pre-polymer mixture comprises a solvent and a polymer; (c) combining the plant-based composition and the curative pre-polymer mixture to form a bio-polymer mixture; (d) applying the bio-polymer mixture to a fiber cloth; and (e) applying heat to the composition of step (d), thereby forming a bio-based leather. i. (a) Preparing a Plant-Based Composition

[0063] In some aspects of the methods of making a bio-based leather disclosed herein, the method comprises (a) preparing a plant-based composition, wherein the plant-based composition comprises vegetal material in powder form.

[0064] In some aspects of the methods of making a bio-based leather disclosed herein, the plant-based composition does not comprise polyurethane (PU) or polyvinyl chloride (PVC). In some aspects of the methods of making a bio-based leather disclosed herein, the plantbased composition does not comprise dimethylformamide (DMF).

[0065] In some aspects of the methods of making a bio-based leather disclosed herein, the plant-based composition is 100% vegetal material.

[0066] In some aspects of the methods of making a bio-based leather disclosed herein, the vegetal material is apple.

[0067] In some aspects, the plant-based composition has a particle size of about 10 pm to about 1000 pm. In some aspects, the plant-based composition has a particle size of about 10 pm to about 840 pm. In some aspects of the methods of making a bio-based leather disclosed herein, the plant-based composition has a particle size of about 20 pm to about 1000 pm. In some aspects, the plant-based composition has a particle size of about 75 pm to about 150 pm.

[0068] In some aspects of the methods of making a bio-based leather disclosed herein, the plant-based composition is 100% bio-based.

[0069] In some aspects of the methods of making a bio-based leather disclosed herein, color powder and/or dye is added to the plant-based composition.

[0070] In some aspects of the methods of making a bio-based leather disclosed herein, the plant-based composition is made by drying vegetal material. In some aspects of the methods of making a bio-based leather disclosed herein, dry ing the vegetal material comprises baking the vegetal material. In some aspects of the methods of making a bio-based leather disclosed herein, the vegetal material is crushed prior to the step of drying the vegetal material. In some aspects of the methods of making a bio-based leather disclosed herein, the dried vegetal material is ground to produce a fruit flour.

[0071] In some aspects of the methods of making a bio-based leather disclosed herein, the plant-based composition is made by freeze-drying vegetal material. The plant-based composition can be freeze-dried by any method known in the art, including, but not limited to, the Toption Vacuum Freeze Dryer GZVF Series.

[0072] A freeze drying cycle can have three phases: freezing, primary drying and secondary drying. The first phase, freezing, transitions water in the product from liquid to solid. During primary drying water can be sublimated from the product by increase in the temperature and decrease in vacuum pressure within the drying chamber. The point where approximately 95% of the water has been removed from a lyophilized substance/product is known as the endpoint of primary drying. Following primary drying, secondary drying can be commenced to reduce further water remaining in the product through increasing temperature and vacuum pressures. The endpoint of primary drying can be determined through comparative pressure measurement (Pirani gauge vs. Capacitance Manometer). Throughout the drying step, the chamber capacitance monometer controls chamber pressure through measurement of the absolute pressure of the drying chamber. The Pirani gauge, which is also located in the drying chamber, measures pressure of the chamber through thermal conductivity of the gases within the chamber. During primary drying, i.e. when water vapor makes up a large percentage of the gas in the chamber, the reading of Pirani gauge can be approximately 60% higher than the capacitance manometer as water vapor thermal conductivity is approximately 1.6 times the thermal conductivity' of air (at -20°C). As the vacuum increases in the drying chamber, the Pirani pressure increases due to the sublimation of water. The point on the lyophilization graph where Pirani pressure decreases sharply indicating the transfer of water from a gaseous state in the chamber to a solid state, ice, on the condenser is the start of bulk water removal from the product. It can be approximated that when the Pirani pressure is equal to the chamber capacitance monometer pressure (absolute chamber pressure) all gaseous water has been removed from the chamber and the primary drying stage is complete. ii. (b) Preparing a Curative Pre-Polymer Mixture

[0073] In some aspects of the methods of making a bio-based leather disclosed herein, the method comprises (b) preparing a curative pre-polymer mixture, wherein the curative prepolymer mixture comprises a solvent and a polymer.

[0074] In some aspects of the methods of making a bio-based leather disclosed herein, the solvent is a poly functional carboxylic acid. In some aspects of the methods of making a biobased leather disclosed herein, the polyfunctional carboxylic acid is citric acid, tartaric acid, succinic acid, malic acid, maleic acid, and/or fumaric acid.

[0075] In some aspects of the methods of making a bio-based leather disclosed herein, the polymer is an epoxidized polymer. In some aspects of the methods of making a bio-based leather disclosed herein, the epoxidized polymer is epoxidized natural rubber (ENR) or epoxidized vegetable oil. In some aspects of the methods of making a bio-based leather disclosed herein, the epoxidized polymer comprises about 25% epoxidation.

[0076] In some aspects of the methods of making a bio-based leather disclosed herein, color powder and/or dye is added to the curative pre-polymer mixture. Examples of dyes include, but are not limited to, pigments, such as pearl pigments, viridian, cobalt blue, cadmiums, magnesium ferrite, red iron oxide, black iron oxide, titanium oxide, zinc iron chromite, manganese, yellow iron oxide, brown iron oxide, ultramarine, bismuth yellow, iron blue, cobalt yellow, mercuric sulfide, and mixtures thereof.

[0077] In some aspects of the methods of making a bio-based leather disclosed herein, the curative pre-polymer is mixed at a temperature of about 30° C to about 50° C. In some aspects of the methods of making a bio-based leather disclosed herein, the curative prepolymer is mixed at a temperature of about 30° C. In some aspects of the methods of making a bio-based leather disclosed herein, the curative pre-polymer is mixed at a temperature of about 35° C. In some aspects of the methods of making a bio-based leather disclosed herein, the curative pre-polymer is mixed at a temperature of about 40° C. In some aspects of the methods of making a bio-based leather disclosed herein, the curative pre-polymer is mixed at a temperature of about 45° C. In some aspects of the methods of making a bio-based leather disclosed herein, the curative pre-polymer is mixed at a temperature of about 50° C. iii. (c) Combining the Plant-Based Composition and the Curative Pre-Polymer Mixture to Make a Bio-Polymer Mixture

[0078] In some aspects of the methods of making a bio-based leather disclosed herein, the method further comprises (c) combining the plant-based composition and the curative prepolymer mixture to form a bio-polymer mixture.

[0079] In some aspects of the methods of making a bio-based leather disclosed herein, color powder and/or dye is added to the bio-polymer mixture.

[0080] In some aspects of the methods of making a bio-based leather disclosed herein, the method further comprises adding zinc salts of organic acids either immediately before, during or immediately after step (c). iv. (d) Applying the Bio-Polymer Mixture to a Fiber Cloth

[0081] In some aspects of the methods of making a bio-based leather disclosed herein, the method further comprises (d) applying the bio-polymer mixture to a fiber cloth.

[0082] In some aspects of the methods of making a bio-based leather disclosed herein, the fiber cloth is cotton, bamboo or jute. [0083] In some aspects of the methods of making a bio-based leather disclosed herein, the step of applying the bio-polymer mixture to a fiber cloth comprises spreading or rolling the bio-polymer mixture on the fiber cloth.

[0084] In some aspects of the methods of making a bio-based leather disclosed herein, after step (d) and before step (e), the bio-polymer mixture is allowed to sit on the fiber cloth for a period sufficient to allow the bio-polymer mixture to wick into the fiber cloth. In some aspects of the methods of making a bio-based leather disclosed herein, the period sufficient to allow the bio-polymer mixture to wick into the fiber cloth is about 1 hour to about 24 hours. v. (e) Applying Heat to the composition of step (d)

[0085] In some aspects of the methods of making a bio-based leather disclosed herein, the method further comprises (e) applying heat to the composition of step (d), thereby forming a bio-based leather.

[0086] In some aspects of the methods of making a bio-based leather disclosed herein, step (e) comprises applying heat to the composition of step (d) at a temperature of 60° C to 100° C for a period of 4 to 24 hours.

[0087] In some aspects of the methods of making a bio-based leather disclosed herein, step (e) comprises applying heat to the composition of step (d) at a temperature of 70° C to 90° C for a period of 4 to 24 hours.

[0088] In some aspects of the methods of making a bio-based leather disclosed herein, during or after step (e), the bio-based leather is processed through a metal mold to produce textures or designs embossed directly onto the coated material.

EXAMPLES

[0089] It is understood that the disclosed method and compositions are not limited to the particular methodology, protocols, and reagents described as these may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention which will be limited only by the appended claims.

[0090] Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the method and compositions described herein. Such equivalents are intended to be encompassed by the following claims.

Example 1: Making a Bio-Based Leather

Preparation of Apple Flour [0091] First, the apple waste will be collected and inserted into a machine to mash it up to create particles. Next, the particles will placed on a tray and the tray will be placed in an oven for 30-45 minutes until the particles are dry. They will be allowed to cool to room temperature for about an hour. Next, the fruit particles will be put into a grinder to produce fine fruit powder (also referred to as flour). Finally, the fruit powder will be placed in a separate metal container.

Preparation of Curative Pre-Polymer Mixture

[0092] In a separate large mixer machine, ENR-25 (Epoxidized natural rubber, a commercially available product under the trade name Epoxyprene® by Sanyo Corp) and either epoxidized soybean oil or castor oil will be added and mixed.

Making the Bio-Polymer Mixture

[0093] In the same mixing container above, the apple flour will be slowly added to the curative pre-polymer mixture. Next, color/dye will be added as either a powder or a liquid. The bio-polymer mixture will be mixed for approximately 20 minutes until the color of mixture is as desired and the texture is even.

Processing the Bio-Polymer Mixture onto Release Paper & Curing

[0094] On a large coagulation machine, either white or beige color release paper will be threaded through the machines (several paper rolls at a time, approximately 40 grams). The bio-polymer mixture will be poured into the coagulation machine. The machines will evenly and slowly apply the bio-polymer mixture onto the paper. The process may be performed in as little as 1 hour or as many as 20 hours depending on the volume.

[0095] The paper with the coating resin will be inserted into a baking oven through textile feeder I cylinder tubes and allowed to cure for approximately 1 hour at 60 °C - 100 °C. Next, the coated paper will be allowed to cool down on the same machine (baking oven).

[0096] Finally, a layer of bio polymer adhesion will be applied on the coagulated paper on the cylinder using a tool similar to a ladle.

Adding the Backing fabric (Fiber Cloth)

[0097] First, the appropriate textile will be threaded through the cylinder machine feeder. Next, the coagulated paper will be threaded through the same machine on top of the textile. The textile and coagulated paper will be processed through another baking oven for bonding. Finally, the paper will be separated from the bonded textile and discarded.

Embossing

[0098] The backing fabric and coagulated paper process will be performed as above, except that a stamped cylinder with the desired texture will used to thread the cured textile. Example 2: Making a Curative Pre-Polymer Mixture

[0099] The following items were added to a 300mL beaker to make the curative prepolymer mixture: First, a piece of approximately 3" solid ENR 25 was placed in the beaker. Next, approximately 50 mL of ethanol was added to the beaker. Next, approximately 30 mL of citric acid powder was added. Then, approximately 60mL of soybean oil was added. The beaker was placed on a hot plate on medium temperature for about 60 - 90 minutes and stirred until all components formed a thick uniform liquid.

[00100] It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.

Claims

CLAIMS We claim:

1. A bio-based leather comprising

(a) a bio-polymer mixture comprising: i. about 25% to about 60% of a plant-based composition comprising vegetal material; and ii. about 40% to about 75% of a curative pre-polymer mixture; and

(b) a fiber cloth.

2. The bio-based leather of claim 1, wherein the bio-based leather does not comprise polyurethane (PU) or polyvinyl chloride (PVC).

3. The bio-based leather of claim 1 or claim 2, wherein the bio-based leather is 100% plant-based material.

4. The bio-based leather of any one of claims 1 to 3, wherein the plant-based composition is about 100% plant-based material or 100% plant-based material.

5. The bio-based leather of any one of claims 1 to 4, wherein the vegetal material is apple.

6. The bio-based leather of any one of claims 1 to 5, wherein the curative pre-polymer mixture comprises an epoxidized polymer.

7. The bio-based leather of claim 6, wherein the epoxidized polymer is epoxidized natural rubber (ENR) or epoxidized vegetable oil.

8. The bio-based leather of claim 6 or claim 7, wherein the epoxidized polymer comprises about 25% epoxidation.

9. The bio-based leather of any one of claims 1 to 8. wherein the fiber cloth is cotton, bamboo, jute or microfiber.

10. The bio-based leather of any one of claims 1 to 9, wherein the bio-based leather further comprises zinc salts of organic acids.

11. The bio-based leather of any one of claims 1 to 10, wherein the bio-based leather has a weight of about 250 g/m² to about 570 g/m²

12. The bio-based leather of any of one of claims 1 to 11, wherein the bio-based leather has a thickness of about 0.5 mm to about 1.2 mm.

13. The bio-based leather of any one of claims 1 to 12, wherein the bio-based leather has a tensile strength along the grain of greater than about 280, greater than about 300, greater than about 350. or greater than about 500 N/5cm.

14. The bio-based leather of any one of claims 1 to 13, wherein the bio-based leather has a tensile strength across the grain of greater than about 15, greater than about 80, greater than about 120, greater than about 500, greater than about 600 or greater than about 650 N/5cm.

15. The bio-based leather of any one of claims 1 to 14, wherein the bio-based leather has a max elongation along the grain of greater than about 13%, greater than about 15%, greater than about 20%, greater than 30% or greater than about 100%.

16. The bio-based leather of any one of claims 1 to 15, wherein the bio-based leather has a max elongation across the grain of greater than about 13%, greater than about 20%, greater than about 30%, greater than about 100%, greater than about 110% or greater than about 250%.

17. The bio-based leather of any one of claims 1 to 16, wherein the bio-based leather has a tear strength along the grain of greater than about 10N, greater than about 12N, greater than about 15N, or greater than about 25N.

18. The bio-based leather of any one of claims 1 to 17, wherein the bio-based leather has a tear strength across the grain of greater than about 7N, greater than about 10N, greater than about 12N, greater than about 15N, greater than about 20N, or greater than about 3 ON.

19. The bio-based leather of any one of claims 1 to 18, wherein the bio-based leather has an adhesion along the grain of greater than about 7 N/5cm, greater than about 15 N/5cm, greater than about 20 N/5cm, greater than about 25 N/5cm, greater than about 30 N/5cm, or greater than about 35 N/5cm.

20. The bio-based leather of any one of claims 1 to 19, wherein the bio-based leather has an adhesion across the grain of greater than about 3 N/5cm, greater than about 20 N/5cm. greater than about 25 N/5cm, greater than about 30 N/5cm. or greater than about 35 N/5cm.

21. The bio-based leather of any one of claims 1 to 20, wherein the bio-based leather has flexometries of greater than 100.000 cycles, greater than 120,000 cycles, or greater than 150,000 cycles.

22. The bio-based leather of any one of claims 1 to 21, wherein the bio-based leather has abrasion resistance of greater than about 6,400 cycles, greater than about 51,200 cycles, greater than about 60,000 cycles, or greater than about 100,000 cycles.

23. The bio-based leather of any one of claims 1 to 22, wherein the bio-based leather has a color fastness of 4/5 or 5/5.

24. The bio-based leather of any one of claims 1 to 23, wherein the bio-based leather comprises a microencapsulated fragrance.

25. A method of making a bio-based leather comprising:

(a) preparing a plant-based composition, wherein the plant-based composition comprises vegetal material in powder form; (b) preparing a curative pre-polymer mixture, wherein the curative pre-polymer mixture comprises a solvent and a polymer;

(c) combining the plant-based composition and the curative pre-polymer mixture to form a bio-polymer mixture;

(d) applying the bio-polymer mixture to a fiber cloth; and

(e) applying heat to the composition of step (d), thereby forming a bio-based leather.

26. The method of claim 25, wherein the plant-based composition does not comprise polyurethane (PU) or polyvinyl chloride (PVC) or dimethylformamide (DMF).

27. The method of claim 25 or claim 26, wherein the plant-based composition is 100% vegetal material.

28. The method of claim 27, wherein the vegetal material is apple.

29. The method of any one of claims 25 to 28, wherein the bio-polymer mixture comprises about 25% to about 60% plant based composition and about 40% to about 75% curative pre-polymer mixture.

30. The method of any one of claims 25 to 29, wherein the plant-based composition has a particle size of about 20 pm to about 1000 pm.

31. The method of any one of claims 25 to 30, wherein the plant-based composition is 100% bio-based.

32. The method of any one of claims 25 to 31. wherein the solvent is a polyfunctional carboxylic acid.

33. The method of claim 32. wherein the polyfunctional carboxylic acid is citric acid, tartaric acid, succinic acid, malic acid, maleic acid, and/or fumaric acid.

34. The method of claim 33, wherein the polyfunctional carboxylic acid is citric acid.

35. The method of any one of claims 25 to 34, wherein the polymer is an epoxidized polymer.

36. The method of claim 35, wherein the epoxidized polymer is epoxidized natural rubber (ENR) or epoxidized vegetable oil.

37. The method of claim 35 or claim 36, wherein the epoxidized polymer comprises about 25% epoxidation.

38. The method of any one of claims 25 to 37. further comprising adding a color powder and/or dye at step (a), step (b) or step (c).

39. The method of any one of claims 25 to 38, wherein the bio-polymer mixture further comprises color powder and/or dye.

40. The method of any one of claims 25 to 39, wherein the fiber cloth is cotton, bamboo, jute or microfiber.

41. The method of any one of claims 25 to 40. wherein the step of applying the biopolymer mixture to a fiber cloth comprises spreading or rolling the bio-polymer mixture on the fiber cloth.

42. The method of any one of claims 25 to 41, wherein step (e) comprises applying heat to the composition of step (d) at a temperature of 60° C to 100° C for a period of 4 to 24 hours.

43. The method of claim 42, wherein step (e) comprises applying heat to the composition of step (d) at a temperature of 70° C to 90° C for a period of 4 to 24 hours.

44. The method of any one of claims 25 to 43, wherein the method further comprises adding zinc salts of organic acids either immediately before, during or immediately after step (c).

45. The method of any one of claims 25 to 44, wherein after step (d) and before step (e), the bio-polymer mixture is allowed to sit on the fiber cloth for a period sufficient to allow the bio-polymer mixture to wick into the fiber cloth.

46. The method of claim 45, wherein the period sufficient to allow the bio-polymer mixture to wick into the fiber cloth is about 1 hour to about 24 hours.

47. The method of any one of claims 25 to 46, wherein during or after step (e), the biobased leather is processed through a metal mold to produce textures or designs embossed directly onto the coated material.