Biobased glove

Abstract

A polymer glove is disclosed that includes one or more polymer layers covering the fingers and palm of a user's hand, wherein at least one polymer layer comprises greater than or equal to about 1 wt% of a bio-based material other than natural rubber or a derivative thereof. Methods of producing the glove are also disclosed.

Description

[0001] This application relates to and claims priority to U.S. Provisional Application No. 63 / 548,099, entitled “Bio-based Gloves,” filed November 10, 2023, which is incorporated herein by reference in its entirety. Technical Field

[0002] This disclosure generally relates to protective articles, and more specifically, to protective articles comprising a protective polymer layer, such as gloves and / or other wearable articles, at least a portion of which is derived from biologically produced material. Background Technology

[0003] Protective equipment worn in industrial and / or home environments (such as gloves, sleeves, etc.) has a polymer barrier layer on it. However, such products typically do not include materials derived from bio-based feedstocks, and therefore lack overall sustainability based almost entirely on petrochemicals.

[0004] While gloves and other protective equipment are required in most industrial environments, the demand for polymer gloves and other protective equipment continues to grow. There is a need to improve the sustainability of raw materials used in the production of protective equipment and to increase the biocompatibility of polymer gloves and other protective equipment, thereby reducing the amount of waste generated.

[0005] In view of the above, the inventors have invented a polymer glove that includes bio-based materials other than natural rubber or its derivatives, thereby improving the sustainability of raw materials used in the production of the glove and reducing the amount of landfill waste due to the bio-content of the material. Summary of the Invention

[0006] This summary is provided to introduce some concepts that will be further described in the following detailed description. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to help limit the scope of the claimed subject matter. In some embodiments, the polymer glove comprises one or more polymer layers covering the user's fingers and palm, and in some embodiments, covering the user's wrist and forearm, wherein at least one polymer layer comprises greater than or equal to about 1 wt% and less than or equal to about 25 wt% of a bio-based material other than natural rubber or derivatives thereof and about 75 wt% to about 99 wt% of an elastomer composition, and a method of manufacturing such a glove, substantially as illustrated and / or described in conjunction with at least one figure, as more fully set forth in the claims. Various advantages, aspects, and novel features of this disclosure, and details of the embodiments shown herein, will be more fully understood from the following description and figures. Attached Figure Description

[0007] To gain a more detailed understanding of the above-described features of the embodiments of this disclosure, reference can be made to a more specific description of the embodiments briefly outlined above, some of which are illustrated in the accompanying drawings. However, it should be noted that the drawings are merely illustrative embodiments of this disclosure and should not be construed as limiting its scope, as the invention disclosed herein may allow for other equivalent embodiments.

[0008] Figure 1 A glove is depicted according to an embodiment disclosed herein.

[0009] Figure 2 A method for forming a glove including a polymer layer according to an embodiment disclosed herein is described. Detailed Implementation

[0010] First, it should be noted that in the development of any such practical implementation, numerous implementation-specific decisions must be made to achieve the developer's specific objectives, such as compliance with system-related and business-related constraints, which will vary depending on the implementation. Furthermore, it should be understood that such development work can be complex and time-consuming, but it remains routine work for those skilled in the art who will benefit from this disclosure. Additionally, the compositions used / disclosed herein may also contain components other than those listed. In the summary and this specific embodiment, each numerical value should first be understood as being modified by the term "about" (unless explicitly stated otherwise), and then as not being modified by it, unless the context otherwise requires. Similarly, each limitation of an embodiment should first be understood as including that embodiment, then as constituting substantially of that embodiment, and then as constituting of that embodiment, unless otherwise stated. For brevity, the term "comprising" is used throughout unless otherwise stated.

[0011] The following definitions are provided to help those skilled in the art understand the specific implementation methods.

[0012] As used herein, “phr” means 100 parts by weight of rubber, unless otherwise stated, where “rubber” refers to an elastomeric polymer. As used herein, bio-based materials are defined as materials derived from natural sources, which may be plant-based or animal-based, including biomass feedstocks and / or the like.

[0013] For the purposes of this article, bio-based materials explicitly exclude natural rubber and its derivatives. For the purposes of this article, according to formula... * 100% accurate determination of the amount of bio-based materials present in the product; in: The quality of bio-based materials does not include any amount of natural rubber and its derivatives that may be present; and The total mass present includes any amount of natural rubber and its derivatives that may be present.

[0014] It should be understood that although natural rubber or its derivatives are explicitly excluded from the molecule, this limitation should not be interpreted as meaning that gloves comprising a minimum amount of bio-based material other than natural rubber or its derivatives do not additionally include natural rubber or its derivatives. For example, embodiments in which at least one polymer layer comprises greater than or equal to about 1 wt% of bio-based material other than natural rubber or its derivatives may, in one embodiment, be free of natural rubber or its derivatives, and in another embodiment, may include natural rubber or its derivatives. Therefore, it should be understood that, for the purposes of this document, polymer gloves comprising at least one polymer layer may also include natural rubber or its derivatives, said polymer layer comprising bio-based material other than natural rubber or its derivatives.

[0015] Bio-based materials are derived from renewable resources or raw materials and include materials of natural origin, used in their naturally occurring form, whether purified (i.e., naturally occurring materials) or chemically modified or otherwise modified and / or derived to produce their derivatives, provided that bio-based materials explicitly do not include natural rubber and its derivatives. For example, polylactic acid polymers are bio-based materials produced through bacterial fermentation of agricultural materials, forming intermediates that are further processed using non-biological systems utilizing non-biological materials to produce the bio-based PLA materials applicable herein.

[0016] While the bio-based materials mentioned herein may be chemically equivalent or substantially equivalent to materials produced from non-biological feedstocks (e.g., petroleum), these materials are produced from bio-based feedstocks. For example, bio-based polyethylene, as a bio-based material applicable herein, may be produced from ethanol derived from agricultural feedstocks, but bio-based polyethylene may be substantially equivalent to polyethylene derived from petroleum. For the purposes of this document, bio-based materials may be used in combination with non-biological based materials.

[0017] For the purposes of this paper, bio-based polymers comprise 10 or more repeating units or portions. For the purposes of this paper, bio-based waxes can be purified from their naturally occurring state, but have a relatively high melting point, suitable hardness, and color, similar to synthetic materials typically characterized as waxes.

[0018] In some embodiments, the polymer gloves are reusable, e.g., suitable for multiple and / or repeated use. In other embodiments, the polymer gloves are sized for single use. In some embodiments, the polymer gloves include one or more polymer layers covering the user's fingers and palms, and in some embodiments, covering the user's fingers, palms, wrists, and forearms, wherein at least one polymer layer comprises an elastomeric material, and wherein at least one polymer layer comprises greater than or equal to about 1 wt% of a bio-based material other than natural rubber or its derivatives.

[0019] In some embodiments, the bio-based material is a naturally occurring material. In some embodiments, the total amount of bio-based material present in at least one polymer layer is less than or equal to about 55 wt%.

[0020] In some embodiments, the elastomeric material is present in at least one polymer layer in an amount of about 75 wt% to about 99 wt%. In some embodiments, the polymer glove comprises multiple polymer layers. In other embodiments, the polymer glove consists essentially of a single polymer layer.

[0021] In some embodiments, the thickness of the polymer glove is from about 0.01 mm to about 0.55 mm. In some embodiments, the thickness of the polymer glove is greater than or equal to about 0.02 mm, or greater than or equal to about 0.04 mm, or greater than or equal to about 0.05 mm, or greater than or equal to about 0.06 mm, or about 0.08 mm, and less than or equal to about 0.55 mm, or less than or equal to about 0.3 mm, or less than or equal to about 0.2 mm, or less than or equal to about 0.18 mm, or less than or equal to about 0.15 mm, or less than or equal to about 0.12 mm.

[0022] In some embodiments, the bio-based material includes polymers, waxes, or combinations thereof. In some embodiments, the bio-based material includes plant-derived waxes. In some embodiments, the bio-based material includes animal-derived waxes. In some embodiments, the bio-based material includes insect-derived waxes. In some embodiments, the bio-based material includes microcrystalline waxes.

[0023] In some embodiments, the bio-based material includes castor wax, candelilla wax, cetacean wax, lanolin wax, jasmine wax, long-chain fatty esters having 12 or more carbon atoms, paraffin wax, beeswax, polyamide wax, carnauba wax, soybean wax, palm wax, bio-based polyethylene wax, or combinations thereof. In some embodiments, the bio-based material includes hydrogenated wax.

[0024] In some embodiments, the bio-based material comprises a blend of two or more bio-based materials. In some embodiments, the bio-based material comprises a blend of three or more bio-based materials.

[0025] In some implementations, bio-based materials include carbohydrates, sugars, starches, polysaccharides, monosaccharides, polylactic acid, polybutylene succinate (PBS), poly(butylene succinate-co-adipate); polyethylene succinate, bio-based polyethylene, or combinations thereof.

[0026] In some embodiments, the elastomer material includes polyisobutylene, polychloroprene, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-propylene rubber, ethylene-propylene diene rubber, natural rubber, polyisoprene, polyurethane, nitrile rubber, carboxylated nitrile rubber, or combinations thereof.

[0027] In some embodiments, the elastomer material is nitrile rubber. In some embodiments, the elastomer material is carboxylated nitrile rubber. In some embodiments, the elastomer material is a combination of nitrile rubber and carboxylated nitrile rubber.

[0028] In some embodiments, the polymer gloves also include pH stabilizers, activators, crosslinking agents, antioxidants, pigments, fillers, or combinations thereof.

[0029] In some embodiments, the polymer gloves are formed from a latex emulsion that is substantially free of curing accelerators. In some embodiments, the polymer gloves are formed from a latex emulsion containing a curing agent. In some embodiments, the polymer gloves are formed from a latex emulsion containing a metal-containing curing agent. In some embodiments, the polymer gloves are formed from a latex emulsion containing a metal oxide curing agent.

[0030] In some embodiments, a method of producing a polymer glove according to any embodiment disclosed herein includes coating a glove mold in an aqueous coagulant solution to produce a coagulant-coated mold; coating the coagulant-coated mold with a latex emulsion comprising an elastomer composition and greater than or equal to about 1 wt% of a bio-based material other than natural rubber or a derivative thereof; curing the latex emulsion coated on the coagulant-coated mold to produce a polymer layer thereon; and obtaining a polymer glove by removing the polymer layer from the mold.

[0031] In some embodiments, at least one layer of the polymer glove comprises greater than or equal to about 1 wt% of a bio-based material other than natural rubber or its derivatives. In some embodiments, at least one layer of the polymer glove comprises greater than or equal to about 1.5 wt%, or greater than or equal to about 2 wt%, or greater than or equal to about 5 wt%, or greater than or equal to about 7 wt%, or greater than or equal to about 10 wt%, or greater than or equal to about 15 wt%, or greater than or equal to about 20 wt% of a bio-based material. In some embodiments, at least one layer of the polymer glove comprises less than or equal to about 50 wt%, or less than or equal to about 40 wt%, or less than or equal to about 30 wt%, or less than or equal to about 25 wt% of a bio-based material.

[0032] In some embodiments, at least one layer of the polymer glove comprises about 1 wt% to about 50 wt%, or 1 wt% to about 40 wt%, or 1 wt% to about 30 wt%, or 1 wt% to about 25 wt% of a bio-based material other than natural rubber or a derivative thereof.

[0033] Bio-based materials In some embodiments, the bio-based material may comprise a bio-based thermoplastic polymer or thermosetting polymer produced from polysaccharides, waxes, and / or naturally derived materials, which may be plant-based or animal-based, including biomass feedstocks and / or the like. Suitable bio-based materials are derived from renewable resources or feedstocks. In some embodiments, one or more bio-based materials may be naturally occurring materials used in their naturally found form, whether or not purified. In some embodiments, one or more bio-based materials may be chemically modified or otherwise modified and / or derived to produce derivatives of the bio-based material.

[0034] In some embodiments, the bio-based material may comprise a polysaccharide, wherein the term "polysaccharide" refers to a molecule having a long chain of monosaccharide units linked together by glycosidic bonds. Suitable polysaccharides can be linear to highly branched. Suitable polysaccharides include naturally occurring polysaccharides found in nature (which may be purified, isolated, or otherwise processed) and / or polysaccharides that have been chemically modified through cross-linking, oxidation, functionalization (e.g., acetylation, partial hydrolysis, hydrogenation, derivatization, and / or similar processes). Suitable examples of bio-based polysaccharides also include gums, hydrocolloids, and / or the like, i.e., polysaccharides that are hydrated in water to form a viscous solution or dispersion.

[0035] In some implementations, suitable polysaccharides include starch and its derivatives, such as amylose, amylopectin, maltodextrin, glucose syrup, glycogen, dextrin, cyclodextrin, cellulose and its derivatives, or other functionalized materials of cellulose, such as methylcellulose, hydroxypropyl methylcellulose, ethylcellulose, cellulose acetate, etc.

[0036] In some implementations, suitable bio-based polysaccharides include plant secretions, also known in the art as plant gums or natural gums. Examples include, but are not limited to, gum arabic (or acacia gum), tragacanth gum, guar gum, locust bean gum, black privet gum, mesquite gum, galactomannan, pectin, soluble soybean polysaccharides, and their extracts.

[0037] In some embodiments, suitable bio-based polysaccharides include marine extracts such as carrageenan and alginate, as well as microbial and / or animal polysaccharides such as gellan gum, dextran, xanthan gum, and chitosan. Suitable bio-based polysaccharides may be homopolysaccharides or may comprise multiple different fractions. In some embodiments, the bio-based material may comprise and / or be derived from starch.

[0038] In some implementations, the bio-based material may comprise a bio-based wax with a relatively high melting point and suitable hardness, color and other physical properties, similar to synthetic materials typically characterized as waxes.

[0039] In some embodiments, the bio-based material includes plant-derived waxes. In some embodiments, the bio-based material includes animal-derived waxes. In some embodiments, the bio-based material includes insect-derived waxes. In some embodiments, the bio-based material includes microcrystalline waxes.

[0040] In some embodiments, the bio-based material includes castor wax, candelilla wax, cetacean wax, lanolin wax, jasmine wax, long-chain fatty esters having 12 or more carbon atoms, paraffin wax, beeswax, polyamide wax, carnauba wax, soybean wax, palm wax, bio-based polyethylene wax, or combinations thereof. In some embodiments, the bio-based material includes hydrogenated wax. In some embodiments, the bio-based material is provided in the form of a wax-based emulsion. In some embodiments, the bio-based wax is a high-triglyceride wax derived from the processing of natural oil-bearing commodities such as soybean, palm, castor, rapeseed, and other crops from which oil can be obtained. In some embodiments, the bio-based wax includes palm oil wax, soybean wax, castor wax, or combinations thereof, which are hydrogenated in some embodiments.

[0041] In some embodiments, the bio-based material may include a bio-based polymer. Suitable bio-based polymers include poly(ε-caprolactone) (PCL), polyhydroxyalkanoates (PHAs) (e.g., polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polyhydroxybutyrate-polyhydroxyvalerate copolymer (PHBV) or derivatives thereof), polybutylene succinate (PBS), polybutylene adipate (PBSA), polylactic acid (PLA), polybutylene terephthalate (PBAT), polydioxanone (PDO), polyglycolic acid (PGA), polybutylene adipate (PBA), polyvinyl alcohol (PVOH), derivatives thereof, and / or mixtures thereof.

[0042] In some implementations, bio-based materials may include bioplastics, which are similar to materials currently derived from petroleum but based on renewable resources. Examples include bio-based PVC, PE, PP, PET, nylon, and polyamide (PA), which are formed from starting monomers obtained from biological resources.

[0043] In some implementations, the bio-based polymer may include polyesters, which are polymers containing ester functional groups in their backbone. Examples of bio-based polyesters include polylactic acid, polyethylene terephthalate, etc.

[0044] In some embodiments, the polymer gloves also include pH stabilizers, activators, crosslinking agents, antioxidants, pigments, fillers, or combinations thereof.

[0045] In some embodiments, the polymer gloves may further include fillers comprising bio-based materials. The fillers may be selected from inorganic or organic fillers. In some embodiments, inorganic fillers include calcite, carbonates, or metal carbonates, such as calcium carbonate (or limestone), potassium carbonate, magnesium carbonate, aluminum carbonate, zinc carbonate, copper carbonate, chalk, dolomite; silicates, such as hydrated magnesium silicate (e.g., talc or soapstone), calcium silicate (wollastonite), potassium silicate, magnesium silicate (talc), aluminum silicate (kaolin), or mixtures thereof, such as mica; montmorillonite, such as montmorillonite, vermiculite, and attapulgite-sepiolite; and sulfates, such as barium sulfate. Or calcium sulfate (gypsum); mica; hydroxide salts or metal hydroxides, such as calcium hydroxide or potassium hydroxide (potassium), or magnesium hydroxide or aluminum hydroxide or sodium hydroxide (caustic soda); hydrotalcite; metal oxides or oxide salts, such as magnesium oxides or calcium oxides or aluminum oxides or iron oxides, or selected from the group consisting of: copper oxides; clay, asbestos, silica, graphite, carbon black, metal fibers or metal foils, glass fibers, magnetic fillers, aramid fibers, ceramic fibers and their derivatives, or blends / mixtures of these materials, but not limited thereto.

[0046] Alternatively or additionally, in some embodiments, at least one polymer layer of the glove comprises greater than or equal to about 1 wt% of a bio-based filler material, such as wood flour, plant flour, or vegetable flour, such as cereal flour (corn flour, wheat flour, rice flour, soybean flour, nut shell flour, clam shell flour, corn cob, cork flour, rice husk); sawdust; plant fibers, such as flax fiber, wood fiber, hemp fiber, bamboo fiber, chicken feathers and their derivatives, or blends / mixtures of these materials. Naturally occurring polymers may also be used as organic fillers, such as lignin; or polysaccharides, such as cellulose or hemicellulose, starch, sugar, glucose, dextrin, chitin, chitosan and their derivatives, or blends / mixtures of these materials.

[0047] Elastomer materials The elastomeric material forming at least one polymer layer of the glove comprises or is substantially composed of: polyisobutylene, polychloroprene, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-propylene rubber, ethylene-propylene diene rubber, natural rubber, polyisoprene, polyurethane, nitrile rubber (NBR), carboxylated nitrile rubber, polyamide, styrene-butadiene rubber, polyvinyl chloride, acrylic acid, ethylene-vinyl acetate copolymer, polyvinyl acetate, butyl, ethylene-propylene diene rubber, chlorosulfonated polyethylene rubber, or combinations thereof. In some embodiments, the elastomeric material forming at least one polymer layer of the glove comprises or is substantially composed of: acrylonitrile-butadiene rubber (NBR), carboxylated nitrile rubber, or combinations thereof.

[0048] In some implementations, at least a portion of the outer surface of the glove has a textured, pebble, rhomboid, diamond, fish scale, or sandpatch surface.

[0049] latex emulsion In some embodiments, the polymer gloves are formed from a latex emulsion containing greater than or equal to about 1 wt% of bio-based materials, as well as elastomer materials and any additional fillers, pH stabilizers, surfactants, solvents, curing agents, curing accelerators, etc. In some embodiments, the latex emulsion is an aqueous emulsion.

[0050] In some embodiments, the latex emulsion is cured to form a polymer layer from which the glove is formed. Curing can be achieved by a curing accelerator and / or by a curing agent. As used herein, a curing accelerator is a material that increases the reaction rate of a chemical reaction that cures the latex (e.g., vulcanization) to form a polymer glove. In contrast, a curing activator is a material that initiates the curing of the latex.

[0051] In some embodiments, the latex emulsion is substantially free of curing accelerators, but contains a curing agent instead. In some embodiments, the curing agent comprises a metal. In some embodiments, the curing agent comprises, is substantially composed of, or is composed of metal oxides. In some embodiments, the curing agent comprises, is substantially composed of, or is composed of a trivalent metal curing agent containing aluminum or zinc. In some embodiments, the trivalent metal curing agent is zinc oxide.

[0052] In some embodiments, the latex emulsion contains about 0.1 wt% to about 5 wt% of a curing agent, or about 0.5 wt% to about 3 wt% of a curing agent, or about 1 wt% to about 2 wt% of a curing agent.

[0053] In some embodiments, the latex emulsion contains about 0.1 wt% to about 5 wt% of a metal oxide curing agent, or about 0.5 wt% to about 3 wt% of a metal oxide curing agent, or about 1 wt% to about 2 wt% of a metal oxide curing agent.

[0054] In some embodiments, the latex emulsion contains about 0.1 wt% to about 5 wt% of a trivalent metal curing agent, or about 0.5 wt% to about 3 wt% of a trivalent metal curing agent, or about 1 wt% to about 2 wt% of a trivalent metal curing agent.

[0055] In some embodiments, the latex emulsion contains about 0.1 wt% to about 5 wt% of zinc oxide as a curing agent, or about 0.5 wt% to about 3 wt% of zinc oxide as a curing agent, or about 1 wt% to about 2 wt% of zinc oxide as a curing agent.

[0056] In some implementations, the latex emulsion is an aqueous emulsion containing a surfactant or surfactant system.

[0057] In some embodiments, a method of producing gloves according to any one or more embodiments disclosed herein includes: coating a glove mold in an aqueous coagulant solution to produce a coagulant-coated mold; coating the coagulant-coated mold with a latex emulsion comprising one or more elastomers; and greater than or equal to about 5 wt% of a bio-based material; curing the aqueous emulsion coated on the coagulant-coated mold to produce a polymer layer thereon; and obtaining gloves according to any one or more embodiments disclosed herein by removing the polymer layer from the mold.

[0058] In an embodiment of the method, coating the coagulant-coated mold with latex emulsion includes drying the latex emulsion on the coagulant-coated mold and coating the dried rubber on the coagulant-coated mold with a second layer of the same or different latex emulsion.

[0059] In some embodiments, the glove comprises multiple polymer layers. In other embodiments, the glove is formed from a single polymer layer.

[0060] In some embodiments, the thickness of the glove is greater than or equal to about 0.05 mm to about 0.55 mm. In some embodiments, the average thickness of the glove is about 0.2 mm to about 0.55 mm.

[0061] In some embodiments, the gloves are configured for single use and have a thickness greater than or equal to about 0.001 mm to about 0.5 mm. In some embodiments, the average thickness of the disposable gloves is about 0.08 mm to about 0.12 mm.

[0062] Figure 1 An unsupported glove 100 formed from a single polymer layer according to an embodiment of the present disclosure is depicted. Although shown as an unsupported glove, the embodiments disclosed herein are also applicable to supported gloves. Glove 100 includes a little finger 106, a ring finger 108, a middle finger 110, an index finger 112, a thumb 114, a palm portion 116, and may optionally include, for example, a support glove 100. Figure 1 The beaded cuff 118 is shown. In an alternative embodiment, the glove extends to cover the user's wrist and at least a portion of the forearm (not shown). The unsupported glove 100 includes at least one polymer layer 120.

[0063] In some embodiments, polymer layer 120 comprises acrylonitrile butadiene rubber. In other embodiments, the polymer layer comprises blends of different acrylonitrile butadiene rubbers, such as carboxylated acrylonitrile butadiene, highly carboxylated acrylonitrile butadiene, non-carboxylated acrylonitrile butadiene, and / or elastomers derived from acrylonitrile and butadiene, having different average molecular weights, different relative compositions or ratios of acrylonitrile and butadiene portions, etc. In other embodiments, polymer layer 120 comprises one or more blends of acrylonitrile butadiene rubber with other elastomers. For example, according to embodiments of this disclosure, polymer layer 120 may also comprise a natural polymer layer or a synthetic polymer layer, or a mixture or blend thereof. The polymer layer 120 may include natural latex, such as guayule or natural rubber, chlorosulfonated polyethylene rubber, ethylene propylene diamine rubber; synthetic latex, such as synthetic polyisoprene, acrylic acid, butyl latex, polychloroprene, waterborne polyurethane and / or non-waterborne polyurethane, styrene-butadiene, polyamide (e.g., nylon), or mixtures or blends thereof. In at least one embodiment, the polymer layer 120 comprises a highly carboxylated acrylonitrile-butadiene latex, which in some embodiments is approximately 35-40 wt% carboxylated.

[0064] Figure 2A method 200 for forming a glove according to an embodiment of the present disclosure is depicted, the glove comprising one or more polymer layers covering a user's fingers and palm, wherein at least one polymer layer comprises an elastomeric material, and wherein at least one polymer layer comprises greater than or equal to about 5 wt% of a bio-based material other than natural rubber or derivatives thereof, for example, comprising polymer layer 120. At block 202, method 200 begins with an unprocessed hand-shaped mold. In some embodiments, the mold (block 201) is heated prior to proceeding to block 204.

[0065] In block 204, the mold is coated with a coagulant, for example, by immersing the mold in a bath of coagulant solution. The coagulant solution can also be applied thereto, for example, by spraying. As known to those skilled in the art, the coagulant solution can be a mixture of water or alcohol containing 3-40% calcium citrate, calcium nitrate, calcium chloride, acetic acid, formic acid, and / or other salts and / or other concentrations. The coagulant is then dried on the mold into coagulant particles. In at least one embodiment, the coagulant solution is heated, for example, to a temperature range of about 42°C to 75°C. In some embodiments, excess coagulant solution on the liner and / or mold is allowed to drip dry by rotating the liner and / or mold so that the finger portions of the mold are facing upwards and allowing it to dry.

[0066] In block 206, an unprocessed mold is immersed in a polymer or elastomer composition according to an embodiment disclosed herein, forming a polymer layer (elastomer layer) thereon. In some embodiments, the polymer or elastomer composition comprises acrylonitrile butadiene rubber. In other embodiments, the polymer composition comprises blends of different acrylonitrile butadiene rubbers, such as carboxylated acrylonitrile butadiene, highly carboxylated acrylonitrile butadiene, non-carboxylated acrylonitrile butadiene, and / or elastomers derived from acrylonitrile and butadiene, having different average molecular weights, different relative compositions or ratios of acrylonitrile and butadiene portions, etc. In other embodiments, the polymer composition comprises one or more blends of acrylonitrile butadiene rubber with other elastomers. The polymer composition according to embodiments of this disclosure may also comprise a natural polymer composition or a synthetic polymer composition or a mixture or blend thereof. The polymer composition may include natural latex, such as guar gum or natural rubber; synthetic latex, such as synthetic polyisoprene, acrylic acid, butyl latex, polychloroprene, waterborne polyurethane and / or non-waterborne polyurethane, styrene-butadiene, polyamide (e.g., nylon), styrene-butadiene rubber, polyvinyl chloride, acrylic acid, ethylene-vinyl acetate copolymer, polyvinyl acetate, butyl, ethylene-propylene rubber, chlorosulfonated polyethylene rubber, etc., or mixtures or blends thereof. In at least one embodiment, the polymer composition comprises a highly carboxylated acrylonitrile-butadiene latex, which in some embodiments is about 35-40 wt% carboxylated.

[0067] As those skilled in the art will know, immersion can be palm immersion, finger immersion, knuckle immersion, or complete immersion. The polymer layer can be dripped, i.e., fingers pointing downwards, to allow excess immersion composition to drip off, thereby reducing the thickness of the polymer layer formed thereon. At block 208, solvents present in the polymer composition on the layer of the mold (if any) are removed, for example, by drying, which can be performed at ambient temperature or high temperature, ambient pressure or low pressure, air-assisted drying, or any combination thereof. Solvent removal can also be performed in one or more stages, each with different conditions. In some embodiments, the mold on which the polymer layer is disposed is rotated so that the polymer layer can be dried in ambient air for several minutes. In at least one embodiment, the polymer layer is dried for approximately one hour.

[0068] In some embodiments, the polymer coating can be leached or washed with an aqueous solution or water at an appropriate temperature (box 209). The mold can be washed before coating with the coagulant, and / or a release layer can be applied to the mold before applying the coagulant to facilitate removal of the glove from the mold after it has been formed.

[0069] In block 210, one or more polymer layers are cured to cure the polymer layers. In some embodiments, for example, the polymer layers are cured in a temperature range of 60°C to 160°C. In some embodiments, for example, the polymer layers are cured at 70°C for about 10 minutes to 3 hours. In some embodiments, the curing block includes curing in an oven (e.g., an infrared oven) and may also include multiple curing temperatures, for example, curing at 70°C for about 10 to 20 minutes in a first curing stage, curing at 100°C for about 10 to 20 minutes, and curing at 160°C for about 10 to 20 minutes, wherein a cured glove is formed.

[0070] In some embodiments, the curing frame 210 isothermally cured for a period of time. In other embodiments, the curing frame 210 is cured in stages at different temperatures for the same or different time periods.

[0071] If the glove consists essentially of a single polymer layer, then in step 212, the polymer layer present on the curing mold is cured. In embodiments where the glove comprises multiple polymer layers, part of method 200 is repeated.

[0072] For example, a first polymer layer may be formed in block 206, followed by solvent removal in block 208 and optionally washing in 209. This portion of the starting method 200 may then be repeated once or multiple times from the immersion in block 206 (indicated by 207A), wherein the coating mold is again immersed in the same or different polymer compositions to form any number of subsequent polymer layers thereon.

[0073] In some embodiments, a first polymer layer may be formed in block 206, followed by solvent removal in block 208 and optionally washing 209, and then the layer may be cured (block 210). This portion of the starting method 200 may then be repeated once or multiple times from the immersion in block 206 (indicated by 207B), wherein the coating mold is again immersed in the same or different polymer composition to form any number of subsequent cured polymer layers thereon (block 210).

[0074] In block 211, the glove is then removed from the mold, which in some embodiments is done by inverting the mold. In some embodiments, the method further includes beading the polymer layers to form a cuff before removing the disposable glove from the mold. In some embodiments, the glove is also chlorinated (block 212) while it is still on the mold during at least one block of the process, or after the glove has been removed from the mold (block 211). In some embodiments, chlorination includes immersing the glove in or otherwise contacting it with a chlorinated aqueous solution for a period of time sufficient to at least partially chlorinate the polymer layers of a single-layer glove, or one or more polymer layers of a multi-layer glove. In one embodiment, the chlorinated aqueous solution contains 500 to 15,000 ppm of chlorine. In another embodiment, the chlorinated aqueous solution contains 1,000 to 10,000 ppm of chlorine. In some embodiments, the glove may undergo multiple chlorination processes at different blocks of the production process and after the glove has been removed from the mold. In block 213, method 200 ends.

[0075] In some embodiments, a method for producing gloves according to embodiments disclosed herein is carried out using equipment suitable for implementing the method, said equipment including one or more controllers, conveyors, molds, cans, ovens, etc. In some embodiments, the mold may be metal or ceramic and is typically hand-shaped. The mold may be arched, such as a partially closed hand, or flat. Furthermore, some of the foregoing steps may be omitted or performed in a different order. In some embodiments, additional processes may be applied prior to curing. Additionally, other steps may be employed.

[0076] For example, in some embodiments, after latex impregnation, the process includes immersion in a polymer coating and / or adhesive, followed by lint. In some embodiments, after curing, the uncured polymer layer on the mold can be peeled off, washed, and dried. Washing can be performed at a temperature of approximately 25°C to 60°C for approximately 15 to 90 minutes (up to 110 minutes for chemical gloves). The gloves can be dried in a tumble dryer, for example, at 50°C to 70°C (up to 80°C for chemical gloves) for approximately 20 to 60 minutes (up to 110 minutes for chemical gloves).

[0077] In some embodiments, at least a portion of the outer surface of the glove has a textured surface. In some embodiments, the texturing or wrinkling process may include salt-based texturing applied to a polymer layer, as disclosed in commonly-assigned US Patents 8,522,363 and 7,771,644, each of which is incorporated herein by reference in its entirety. In other embodiments, a disposable glove with a textured outer surface may include a textured outer layer disposed on a portion of a polymer layer to impart texture to the outer surface. In other embodiments, a portion of a mold for producing a disposable glove includes one or more textured portions, the dimensions and arrangement of which are configured to impart a textured surface to a portion of the disposable glove formed using the textured mold. For example, an elastomeric coating cured on a mold, wherein the grip-defining portion of the mold has an average roughness Ra of about 7-14 micrometers, an average roughness width Rsm of about 500-720, and a peak count Rpc of about 15-20, as disclosed in equally-assigned US 10,058,137 B2, the contents of which are incorporated herein by reference. In some embodiments, the glove mold has one or more surfaces in the fingertip region having an average roughness Ra of about 7-14 micrometers, an average roughness width Rsm of about 500-720, and / or a peak count Rpc of about 15-20. In some embodiments, the fingertip region of the glove mold has an average roughness depth Rz of about 30-50 micrometers, a maximum roughness depth Rmax of about 40-70 micrometers, a maximum peak height Rp of about 8-22 micrometers, and / or a maximum valley depth Rv of about 16-35 micrometers, as disclosed in the same assigned US 10,405,593 B2, the contents of which are incorporated herein by reference.

[0078] At least one exemplary embodiment according to this disclosure includes a second polymer layer. For example, a method of manufacturing disposable gloves may further include depositing another polymer layer on the aforementioned mold. The polymer layer may optionally have a coagulant disposed thereon.

[0079] Implementation Plan The implementation scheme according to this disclosure includes: E1. A polymer glove comprising: One or more polymer layers covering the user's fingers and palms. At least one of the polymer layers contains an elastomeric material. And at least one of the polymer layers contains more than or equal to about 1 wt% of bio-based materials other than natural rubber or its derivatives.

[0080] E2. The polymer glove according to embodiment E1, wherein the bio-based material is a naturally occurring material.

[0081] E3. The polymer gloves according to embodiments E1-E2, wherein the total amount of bio-based material present in at least one polymer layer is less than or equal to about 60 wt%.

[0082] E4. The polymer glove according to embodiments E1-E3, wherein the elastomeric material is present in at least one polymer layer in an amount of about 75 wt% to about 99 wt%.

[0083] E5. The polymer gloves according to embodiments E1-E4, which are essentially composed of a single polymer layer.

[0084] E6. The polymer gloves according to embodiments E1-E5, having a thickness of about 0.001 mm to about 0.55 mm.

[0085] E7. The polymer gloves according to embodiments E1-E6, having a thickness of about 0.2 mm to about 0.55 mm.

[0086] E8. The polymer gloves according to embodiments E1-E7, wherein the bio-based material comprises polymers, waxes, or combinations thereof.

[0087] E9. The polymer gloves according to embodiments E1-E8, wherein the bio-based material comprises plant-derived waxes.

[0088] E10. The polymer gloves according to embodiments E1-E9, wherein the bio-based material comprises animal-derived waxes.

[0089] E11. The polymer gloves according to embodiments E1-E10, wherein the bio-based material comprises insect-derived wax.

[0090] E12. The polymer gloves according to embodiments E1-E11, wherein the bio-based material comprises microcrystalline wax.

[0091] E13. The polymer gloves according to embodiments E1-E12, wherein the bio-based material includes castor wax, candelilla wax, cetacean wax, wool wax, Japanese wax, long-chain fatty esters having 12 or more carbon atoms, paraffin wax, beeswax, polyamide wax, carnauba wax, soybean wax, palm wax, bio-based polyethylene wax, or combinations thereof.

[0092] E14. The polymer gloves according to embodiments E1-E13, wherein the bio-based material comprises hydrogenated wax.

[0093] E15. The polymer gloves according to embodiments E1-E14, wherein the bio-based material comprises a blend of two or more bio-based materials.

[0094] E16. The polymer gloves according to embodiments E1-E15, wherein the bio-based material comprises a blend of three or more bio-based materials.

[0095] E17. The polymer gloves according to embodiments E1-E16, wherein the bio-based material comprises carbohydrates, sugars, polysaccharides, monosaccharides, starch, polylactic acid, polybutylene succinate (PBS), poly(butylene succinate-co-adipate); polyethylene succinate, bio-based polyethylene, natural rubber latex, or combinations thereof.

[0096] E18. The polymer gloves according to embodiments E1-E17, wherein the elastomer material comprises polyisobutylene, polychloroprene, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-propylene rubber, ethylene-propylene diene rubber, natural rubber, polyisoprene, polyurethane, nitrile rubber, carboxylated nitrile rubber, polyamide, butyl rubber, polyamide, polyvinyl chloride, polyvinyl acetate, ethylene propylene diene rubber, chlorosulfonated polyethylene rubber, or combinations thereof.

[0097] E19. The polymer gloves according to embodiments E1-E18 further include pH stabilizers, activators, crosslinking agents, antioxidants, pigments, fillers, or combinations thereof.

[0098] E20. The polymer gloves according to embodiments E1-E19, which are formed from a latex emulsion containing a curing accelerator.

[0099] E21. The polymer gloves according to embodiments E1-E20 are formed from a latex emulsion that is substantially free of curing accelerators.

[0100] E22. The polymer gloves according to embodiments E1-E21 are formed from a latex emulsion containing a curing agent.

[0101] E23. The polymer gloves according to embodiments E1-E22 are formed from a latex emulsion containing a curing agent comprising a metal oxide.

[0102] E24. A method for producing polymer gloves according to any one of embodiments E1-E23, comprising: Coating a glove mold with a coagulant aqueous solution to produce a coagulant-coated mold; The coagulant is coated onto the mold with a latex containing an elastomer composition and more than or equal to about 1 wt% and less than or equal to about 60 wt% of a bio-based material other than natural rubber or its derivatives. Curing the latex emulsion coated on the coagulant-coated mold to form a polymer layer thereon; and The gloves according to any one of claims 1 to 24 are obtained by removing the polymer layer from the mold. E25. A method for producing polymer gloves according to embodiment E24, further comprising: after latex impregnation, impregnation into a polymer coating and / or adhesive, followed by impregnation into cotton lint.

[0103] Example Gloves were prepared according to the embodiments disclosed herein, as shown in Table 1, wherein, according to the embodiments disclosed herein, a portion of the formulation was replaced with a bio-based material other than natural rubber or its derivatives. The gloves were then evaluated as shown in Tables 2 and 3 disclosed below. The chemical resistance results are in compliance with EN 374. Mechanical resistance complies with EN388. As the data above shows, the gloves according to the embodiments disclosed herein have performance equivalent to or better than gloves known in the prior art.

[0104] The foregoing disclosure and description of the present invention are illustrative and explanatory, and it will be readily understood by those skilled in the art that various changes may be made to the dimensions, shapes, and materials, as well as to the details of the illustrated construction or combination of the elements described herein, without departing from the spirit of the invention.

Claims

1. A polymer glove comprising: One or more polymer layers covering the user's fingers and palms. At least one of the polymer layers contains an elastomeric material. And the at least one polymer layer therein comprises a bio-based material other than natural rubber or its derivatives.

2. The polymer glove according to claim 1, wherein the bio-based material is a naturally occurring material.

3. The polymer glove of claim 1, wherein the total amount of bio-based material present in at least one polymer layer is greater than or equal to about 1 wt% and less than or equal to about 60 wt%.

4. The polymer glove of claim 1, wherein the elastomeric material is present in at least one polymer layer in an amount of about 75 wt% to about 99 wt%.

5. The polymer glove according to claim 1, which is essentially composed of a single polymer layer.

6. The polymer glove according to claim 1, wherein the thickness is from about 0.001 mm to about 0.55 mm.

7. The polymer glove of claim 1, wherein the bio-based material comprises polymers, waxes, or combinations thereof.

8. The polymer glove of claim 1, wherein the bio-based material comprises plant-derived waxes.

9. The polymer glove of claim 1, wherein the bio-based material comprises waxes derived from animals and / or waxes derived from insects.

10. The polymer glove of claim 1, wherein the bio-based material comprises insect-derived wax.

11. The polymer glove of claim 1, wherein the bio-based material comprises castor wax, candelilla wax, cetacean wax, wool wax, Japanese wax, long-chain fatty esters having 12 or more carbon atoms, paraffin wax, beeswax, polyamide wax, carnauba wax, soybean wax, palm wax, bio-based polyethylene wax, hydrogenated wax, microcrystalline wax, or combinations thereof.

12. The polymer glove of claim 1, wherein the bio-based material comprises a blend of two or more bio-based materials.

13. The polymer glove of claim 1, wherein the bio-based material comprises carbohydrates, sugars, polysaccharides, monosaccharides, starch, polylactic acid, polybutylene succinate (PBS), poly(butylene succinate-co-adipate); polyethylene succinate, bio-based polyethylene, natural rubber latex, or combinations thereof.

14. The polymer glove of claim 1, wherein the elastomer material comprises polyisobutylene, polychloroprene, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-propylene rubber, ethylene-propylene diene rubber, natural rubber, polyisoprene, polyurethane, nitrile rubber, carboxylated nitrile rubber, butyl rubber, polyamide, polyvinyl chloride, polyvinyl acetate, ethylene propylene diene rubber, chlorosulfonated polyethylene rubber, or combinations thereof.

15. The polymer glove of claim 1, further comprising a pH stabilizer, an activator, a crosslinking agent, an antioxidant, a pigment, a filler, or a combination thereof.

16. The polymer glove of claim 1, wherein it is formed from a latex emulsion comprising a curing accelerator.

17. The polymer glove of claim 1, wherein it is formed from a latex emulsion that is substantially free of curing accelerators.

18. The polymer glove of claim 1, wherein it is formed from a latex emulsion containing a curing agent.

19. The polymer glove of claim 1, wherein it is formed from a latex emulsion comprising a curing agent comprising a metal oxide.

20. A method for producing polymer gloves according to any one of the preceding claims, comprising: Coating a glove mold with a coagulant aqueous solution to produce a coagulant-coated mold; The coagulant is coated onto the mold with a latex containing an elastomer composition and more than or equal to about 1 wt% and less than or equal to about 60 wt% of a bio-based material other than natural rubber or its derivatives. Curing the latex emulsion coated on the coagulant-coated mold to form a polymer layer thereon; and The gloves according to any one of claims 1 to 24 are obtained by removing the polymer layer from the mold.

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