Elastomeric chemical barrier articles

Abstract

An elastomeric article having a layered structure, which includes an outer elastomeric barrier layer bonded to a middle elastomeric layer comprising polyvinyl alcohol, which is bonded to an inner elastomeric layer. A method of forming and using the elastomeric article are also disclosed.

Description

ELASTOMERIC CHEMICAL BARRIER ARTICLES

[0001] This application is associated with and claims priority to United States Provisional Application No. 63 / 762,527, filed on 24 February 2025, which is incorporated in its entirety by reference.

[0002] The present application relates generally to elastomeric chemical barrier articles containing a laminate of layers of an outer elastomeric barrier layer, a middle elastomeric layer comprising polyvinyl alcohol, and an inner elastomeric layer.

[0003] To allow a user to handle various tools and objects in a chemical environment, a piece of protective clothing such as a coverall, and / or a glove is provided. The article provides some flexibility and dexterity during its use in addition to providing a high level of protection against dangerous chemical solvents and esters. Generally, prior art barrier materials ensure protection to only very limited number of chemicals and when a user must handle tasks of several other different chemical families, a common solution e.g., of gloves, is overgloving gloves that are resistant to each of these families to form a complimentary protection. An overglove, or overgloving, may be used, for example, as an additional layer of protection, which is disposed on another glove. However, this solution of overgloving is not ergonomically practical in that it hinders handling and makes the composite glove too bulky.

[0004] An available solution to this issue is a plastic typed welded glove, but this type of glove does not possess the good fit, comfort feel, dexterity and flexibility of an elastomeric glove (e.g., nitrile, neoprene or butyl glove). While Nitrile and Neoprene have good protection against non-polar solvents, they have very limited chemical protection against chlorinated solvents such as methylene chloride and the like, and / or aromatic solvents, and / or ethereal solvents such as tetrahydrofuran. Butyl or butyl / viton materials have a slightly more comprehensive range of chemical protection than Nitrile and Neoprene, but still have weaknesses. Therefore, an elastomeric feel glove that has a broader range of chemical protection coverage than Nitrile, Neoprene, Butyl or ButylA / iton gloves has become a sought after product. Provided here is a glove with dexterity and flexibility, but superior performance measured in permeation time against chlorinated and aromatic solvents. Generally, performance against other non-polar and polar solvents is maintained.SUMMARY

[0005] An elastomeric article having a layered structure, in accordance with the various embodiments, substantially as shown in and / or described in connection with at least one of the figures, as set forth more completely in the claims, are disclosed herein. Various advantages, aspects, and novel features of the present disclosure, as well as details of an exemplary embodiment thereof, will be more fully understood from the following description and drawings. Also shown and described are methods of making and using the elastomeric article having a barrier layer.

[0006] I n embodiments, an elastomeric article comprises an outer elastomeric barrier layer bonded to a middle elastomeric layer comprising polyvinyl alcohol, which is bonded to an inner elastomeric layer.

[0007] In embodiments, an elastomeric article having a layered structure comprises an outer elastomeric barrier layer bonded to a middle elastomeric layer comprising polyvinyl alcohol, which is bonded to an inner elastomeric layer, wherein the outer elastomeric barrier layer is formed from an aqueous latexbased colloidally stable rubber lattice comprising natural rubber, chloroprene rubber, butyl rubber, acrylonitrile butadiene rubber, styrene-butadiene rubber, polyurethane, polyisoprene rubber, polyvinyl chloride, polyvinyl alcohol, ethylene vinyl acetate, ethylene propylene diene monomer, chlorosulfonated polyethylene rubber or a combination thereof; wherein the middle elastomeric layer comprises polyvinyl alcohol, or a blend comprising polyvinyl alcohol and one or more of polyvinyl chloride, butyl rubber, ethylene propylene diene monomer (EPDM), chlorosulfonated polyethylene rubber (CSM), or a combination thereof; wherein the inner elastomeric layer comprises polyamide polymer, or a blend comprising polyamide polymer and one or more of acrylic polymer, polyurethane, natural rubber, chloroprene rubber, butyl rubber, acrylonitrile butadiene rubber, styrene-butadiene rubber, polyurethane, polyisoprene rubber, polyvinyl chloride, polyvinyl alcohol, ethylene vinyl acetate, ethylene propylene diene monomer, chlorosulfonated polyethylene rubber, or a combination thereof; and wherein one or more of the layers are disposed by dipping and one or more of the layers are dried and cured after said dipping.

[0008] In embodiments, a method of forming an elastomeric article according to one or more embodiments disclosed herein comprises disposing the outer elastomeric barrier layer over a shaped former; disposing the middle elastomeric layer onto the outer elastomeric barrier layer; disposing the inner elastomeric layer onto the middle elastomeric layer to form the elastomeric article; and removing the elastomeric article from the shaped former by inversion.

[0009] In embodiments, a method of forming an elastomeric article according to one or more embodiments disclosed herein comprises disposing the inner elastomeric layer over a shaped former; disposing the middle elastomeric layer onto the inner elastomeric layer; disposing the outer elastomeric barrier layer onto the middle elastomeric layer to form the elastomeric article; and removing the elastomeric article from the shaped former.

[0010] In embodiments, a method of using an elastomeric article according to one or more embodiments disclosed herein comprises donning a portion of a human at risk of chemical exposure with the article; and wearing the article for a period of time during which there is a risk of such exposure.

[0011] The foregoing summary is not intended, and should not be contemplated, to describe each embodiment or every implementation described in the disclosure. Other and further embodiments are described below.DESCRIPTION OF THE DRAWINGS

[0012] So that the manner in which the above recited features of embodiments of the instant disclosure, can be understood in detail, a more particular description of that briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only illustrative embodiments are therefore not to be considered limiting of its scope, for this disclosure may admit to other equally effective embodiments.

[0013] FIG. 1 depicts a multi-layer structure including the laminate of elastomer (outer elastomeric barrier layer), middle elastomeric layer and polyamide.

[0014] FIG. 2 depicts a polyester structure.

[0015] FIG. 3 depicts a flowchart of a method for making structures of embodiments disclosed herein.

[0016] To facilitate understanding, identical reference numerals have been used, where possible, to designate comparable elements that are common to the figures. The figures are not drawn to scale and may be simplified for clarity. It is contemplated that elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation.DETAILED DESCRIPTION

[0017] The instant disclosure is generally directed to a protective article, which in embodiments is formed by dipping, which in embodiments is a glove including a glove extending over most of the wrist or past the elbow, and the like. In other embodiments the protective article is a coverall, which in embodiments is free of sewn seams, or a portion of a coverall.

[0018] I n embodiments, an elastomeric article comprises an outer elastomeric barrier layer bonded to a middle elastomeric layer comprising polyvinyl alcohol, which is bonded to an inner elastomeric layer. In some of such embodiments, the middle elastomeric layer is a blend comprising polyvinyl alcohol and one or more elastomers present in the outer elastomeric barrier layer, one or more elastomers present in the inner elastomeric layer, or a combination thereof. In embodiments, alone or in combination with other embodiments, the outer elastomeric barrier layer is formed from an aqueous latex-based colloidally stable rubber lattice comprising natural rubber, chloroprene rubber, butyl rubber, acrylonitrile butadiene rubber, styrene-butadiene rubber, polyurethane, polyisoprene rubber, polyvinyl chloride, polyvinyl alcohol, ethylene vinyl acetate, ethylene propylene diene monomer, chlorosulfonated polyethylene rubber or a combination thereof.

[0019] In embodiments, alone or in combination with other embodiments, the outer elastomeric barrier layer comprise greater than 50% by weight butyl, NBR, chloroprene, or blends thereof, and further comprises vinyl polymers comprising oxo (-(C=O)-) groups, each comprising a carbon atom doubled bondedto an oxygen atom. In embodiments, alone or in combination with other embodiments, the outer elastomeric barrier layer is essentially free of polyolefin.

[0020] In embodiments, alone or in combination with other embodiments, the polymers of the outer elastomeric barrier layer are blended with a water dispersible saturated polyester resin, ultrafine high molecular weight polyamide powder, ethylene based copolymer, a hydrophobic wax, or a mixture thereof.

[0021] In embodiments, alone or in combination with other embodiments, the outer elastomeric barrier layer is from about 5 mils to about 20 mils in thickness. In embodiments, alone or in combination with other embodiments, the middle elastomeric layer is from about 0.3 mil to about 10 mils in thickness. In embodiments, alone or in combination with other embodiments, the inner elastomeric layer is from about 0.1 mils to about 5 mils in thickness.

[0022] In embodiments, alone or in combination with other embodiments, the article has a maximum total thickness of less than or equal to about 24 mils (0.61 mm).

[0023] In embodiments, alone or in combination with other embodiments, the outer elastomeric barrier layer comprises a blend of EPDM and neoprene rubber; the middle elastomeric layer comprises polyvinyl alcohol or a blend comprising polyvinyl alcohol and one or more of polyvinyl chloride, butyl rubber, ethylene propylene diene monomer (EPDM), chlorosulfonated polyethylene rubber (CSM), or a combination thereof; and the inner elastomeric layer comprises polyamide polymer; or a blend comprising polyamide polymer and one or more of acrylic polymer, polyurethane, natural rubber, chloroprene rubber, butyl rubber, acrylonitrile butadiene rubber, styrene-butadiene rubber, polyurethane, polyisoprene rubber, polyvinyl chloride, polyvinyl alcohol, ethylene vinyl acetate, ethylene propylene diene monomer, chlorosulfonated polyethylene rubber, or a combination thereof.

[0024] In embodiments, alone or in combination with other embodiments, the middle elastomeric layer further comprises polyethylene, polystyrene, ethylene-vinyl acetate (EVA), ethylene-methyl acrylate (EMA); ethylene-ethyl acrylate (EEA), ethylene vinyl polyester, ethylene grafted maleic anhydride (AMP), or mixtures thereof. In embodiments, alone or in combination with other embodiments, the outer elastomeric barrier layer comprises acrylonitrile butadiene rubber (NBR), also referred to as nitrile rubber, and a water dispersible polyester resin.

[0025] In embodiments, alone or in combination with other embodiments, the inner elastomeric layer comprises nylon 6, nylon 66, nylon 69, nylon 610, nylon 612, or a combination thereof. In some embodiments, alone or in combination with other embodiments, the inner elastomeric layer comprises about 30 to about 75% by weight nylon 6; about 5 to about 80% by weight nylon 66; about 20 to about 55% by weight nylon 69; about 10 to about 80% by weight nylon 610; or about 10 to about 80% by weight nylon 612. In some of such embodiments, alone or in combination with other embodiments, the inner elastomeric layer comprises a terpolymer comprising nylon 6, nylon 66, and nylon 69, wherein the nylon 6 is present at about35 to about 55% by weight, wherein the nylon 66 is present at about 5 to about 35% by weight; and the nylon 69 is present at about 20 to about 55% by weight in the terpolymer. In some of such embodiments, alone or in combination with other embodiments, the inner elastomeric layer comprises a terpolymer comprising nylon 6, nylon 66, and nylon 610, wherein the nylon 6 is present at about 35 to about 75% by weight, the nylon 66 is present at about 10 to about 80% by weight; and the nylon 610 is present at about 10 to about 80% by weight in the terpolymer. In some of such embodiments, alone or in combination with other embodiments, the inner elastomeric layer comprises a terpolymer comprising nylon 6, nylon 66, and nylon 612, wherein the nylon 6 is present at about 30 to about 75% by weight, the nylon 66 is present at about 10 to about 80% by weight; and the nylon 612 is present at about 10 to about 80% by weight in the terpolymer.

[0026] In embodiments, alone or in combination with other embodiments, the outer elastomeric barrier layer comprises chloroprene and hydrophobic wax, and the middle elastomeric layer further comprises EVA copolymer.

[0027] In embodiments, alone or in combination with other embodiments, the outer elastomeric layer comprises less than about 30% by weight of a polyolefin.

[0028] In embodiments, alone or in combination with other embodiments, the inner elastomeric layer comprises one or more polymers formed from monomers selected from the group consisting of caprolactam, adipic acid, azelaic acid, sebacic acid, 1 ,10-decanedicarboxylic acid and hexamethylene diamine.

[0029] In embodiments, alone or in combination with other embodiments, the outer elastomeric barrier layer provides greater than about 50% of a thickness of the article. In some embodiments, alone or in combination with other embodiments, the elastomeric article further includes a coating layer having a thickness of less than or equal to about 5 mils (0.13mm) disposed over the outer elastomeric barrier layer, the inner elastomeric barrier layer, or both. In some of such embodiments, alone or in combination with other embodiments, the coating layer comprises natural rubber, chloroprene rubber, butyl rubber, acrylonitrile butadiene rubber, styrene-butadiene rubber, polyurethane, polyisoprene rubber, polyvinyl chloride, polyvinyl alcohol, ethylene vinyl acetate, ethylene propylene diene monomer, chlorosulfonated polyethylene rubber, or a combination thereof. In some of such embodiments, alone or in combination with other embodiments, the coating layer comprises acrylonitrile butadiene rubber (i.e., nitrile rubber).

[0030] In embodiments, alone or in combination with other embodiments, at least a portion of the inner elastomeric layer is disposed over a woven or non-woven support.

[0031] In embodiments, alone or in combination with other embodiments, an elastomeric article having a layered structure comprises an outer elastomeric barrier layer bonded to a middle elastomeric layer comprising polyvinyl alcohol, which is bonded to an inner elastomeric layer, wherein the outer elastomeric barrier layer is formed from an aqueous latex-based colloidally stable rubber lattice comprising natural rubber,chloroprene rubber, butyl rubber, acrylonitrile butadiene rubber, styrene-butadiene rubber, polyurethane, polyisoprene rubber, polyvinyl chloride, polyvinyl alcohol, ethylene vinyl acetate, ethylene propylene diene monomer, chlorosulfonated polyethylene rubber or a combination thereof; wherein the middle elastomeric layer comprises polyvinyl alcohol, or a blend comprising polyvinyl alcohol and one or more of polyvinyl chloride, butyl rubber, ethylene propylene diene monomer (EPDM), chlorosulfonated polyethylene rubber (CSM), or a combination thereof; wherein the inner elastomeric layer comprises polyamide polymer, or a blend comprising polyamide polymer and one or more of acrylic polymer, polyurethane, natural rubber, chloroprene rubber, butyl rubber, acrylonitrile butadiene rubber, styrene-butadiene rubber, polyurethane, polyisoprene rubber, polyvinyl chloride, polyvinyl alcohol, ethylene vinyl acetate, ethylene propylene diene monomer, chlorosulfonated polyethylene rubber, or a combination thereof; and wherein one or more of the layers are disposed by dipping and one or more of the layers are dried and cured after said dipping.

[0032] In embodiments, alone or in combination with other embodiments, the aqueous latex-based colloidally stable rubber lattice comprises greater than about 50% by weight of the rubber lattice blended in an aqueous elastomeric latex, the rubber lattice comprising natural rubber, chloroprene rubber, butyl rubber, acrylonitrile butadiene rubber, styrene-butadiene rubber, polyurethane, or a combination thereof. In some of such embodiments, alone or in combination with other embodiments, the middle elastomeric layer comprises greater than or equal to about 50.5 % by weight polyvinyl alcohol (PVOH). In embodiments, alone or in combination with other embodiments, two or more of the outer elastomeric barrier layer, the middle elastomeric layer, and the inner elastomeric layer are cured simultaneously. In some of such embodiments, alone or in combination with other embodiments, the outer elastomeric barrier layer is less than 50% by weight polyolefin. In some of such embodiments, alone or in combination with other embodiments, the outer elastomeric barrier layer provides greater than about 50% of a thickness of the article.

[0033] In embodiments, alone or in combination with other embodiments, the layered structure of the elastomeric article is effective to provide a chemical permeation time in excess of 400 minutes pursuant to EN 16523-1:2015 for benchmark solvents of dichloromethane, toluene and tetrahydrofuran. In some of such embodiments, alone or in combination with other embodiments, the permeation time of the elastomeric article, when measured pursuant to EN 16523-1:2015 and compared to a comparative layer of material of the outer elastomeric barrier layer of a thickness of the layered structure, the layered structure is effective to provide a dichloromethane chemical permeation time, an acetone permeation time, an ethyl acetate permeation time, and a methanol permeation time which is greater than a corresponding permeation time for the comparative layer, wherein at least one permeation time is about five-times or greater than the corresponding permeation time of the comparative layer.

[0034] In embodiments, alone or in combination with other embodiments, the elastomeric article is a single use glove. In embodiments, alone or in combination with other embodiments, the elastomeric article is a coverall, or a portion of a coverall, which in embodiments is a coverall without sewn seams.

[0035] In embodiments, alone or in combination with other embodiments, wherein the inner elastomeric layer comprises polyamide, the elastomeric article is an industrial use glove.

[0036] In embodiments, alone or in combination with other embodiments, a method of forming an elastomeric article comprises disposing the outer elastomeric barrier layer over a shaped former; disposing the middle elastomeric layer onto the outer elastomeric barrier layer; disposing the inner elastomeric layer onto the middle elastomeric layer to form the elastomeric article; and removing the elastomeric article from the shaped former by inversion.

[0037] In some of such embodiments, alone or in combination with other embodiments, the method further comprises disposing a coating layer over the shaped former prior to disposing the outer elastomeric barrier layer coating onto the shaped former. In some of such embodiments, alone or in combination with other embodiments, the method further comprises disposing a coating layer over the inner elastomeric layer prior to removing the elastomeric article from the shaped former by inversion.

[0038] In some of such embodiments, alone or in combination with other embodiments, the method further comprises at least one of the outer elastomeric barrier layer, the middle elastomeric layer, and the inner elastomeric layer being disposed by dipping. In some of such embodiments, alone or in combination with other embodiments, the method further comprises two or more of the outer elastomeric barrier layer, the middle elastomeric layer, and the inner elastomeric layer being disposed prior to curing the two or more layers simultaneously.

[0039] In embodiments, alone or in combination with other embodiments, a method forming an elastomeric article comprises disposing the inner elastomeric layer over a shaped former; disposing the middle elastomeric layer onto the inner elastomeric layer; disposing the outer elastomeric barrier layer onto the middle elastomeric layer to form the elastomeric article; and removing the elastomeric article from the shaped former.

[0040] In some of such embodiments, alone or in combination with other embodiments, the method further comprises disposing a coating layer over the shaped former prior to disposing the inner elastomeric layer over the shaped former. In some of such embodiments, alone or in combination with other embodiments, the method further comprises disposing a coating layer over the outer elastomeric barrier layer prior to removing the elastomeric article from the shaped former.

[0041] In some of such embodiments, alone or in combination with other embodiments, the method further comprises disposing a woven or non-woven support over the shaped former prior to disposing the inner elastomeric layer over the shaped former.

[0042] In some of such embodiments, alone or in combination with other embodiments, at least one of the outer elastomeric barrier layer, the middle elastomeric layer, and the inner elastomeric layer are disposed by dipping.

[0043] In some of such embodiments, alone or in combination with other embodiments, two or more of the outer elastomeric barrier layer, the middle elastomeric layer, and the inner elastomeric layer are disposed prior to curing the two or more layers simultaneously.

[0044] In embodiments, a method of using the elastomeric article according to one or more embodiments disclosed herein comprises donning a portion of a human at risk of chemical exposure with the article; and wearing the article for a period of time during which there is a risk of such exposure.

[0045] Exemplary layered structures are shown in FIG. 1. Layer 10 is an outer elastomeric barrier layer, which can be latex-based. In embodiments, this "layer" is comprised of several sublayers (such as by multiple dipping or other coating processes) such as sublayers 10A and 10B. All references herein to layer 10 includes a reference to sublayer 10B. The sublayers may or may not be analytically distinguishable. The sublayers can be of different composition. Layer 12 is a middle elastomeric layer comprising polyvinyl alcohol. In embodiments, the middle elastomeric layer 12 comprises greater than 50 wt% polyvinyl alcohol. Layer 14 is an inner elastomeric layer. Layer 16 can be multiple sublayers of materials or one sublayer. In embodiments, layer 16 is a coating layer. Likewise, in embodiments, layer 8 is a coating layer.

[0046] In embodiments, layer 10 is from about 5 mils (0.13 mm) to about 24 mils (0.61 mm). In embodiments, layer 12 is from about 0.3 mil (0.0076 mm) to about 6 mils (0.15 mm), such as from about 0.5 mils (0.013 mm) to about 3 mils (0.076 mm). In embodiments, layer 14 is from about 0.1 mils (0.0025 mm) to about 5 mils (0.13 mm), such as from about 1.0 mil (0.025 mm) to about 2.0 mils (0.005 mm). Typically, the Layer 10 provides more than 50% of the thickness of the article, and the polymer thereof is thereby the primary polymer.

[0047] In embodiments, coating layers, e.g., layer 8 and layer 16, have a thickness of less than or equal to about 5 mils (0.13 mm), or less than or equal to about 1 mil (0.065 mm), or less than or equal to about 0.5 mils (0.013 mm).

[0048] In embodiments disclosed herein when directed to a non-supported article, i.e., an article without a support substrate, the article is formed by disposing the various components of the layers sequentially over the shaped former. In embodiments, one or more of the layers is disposed by dipping a shaped former into dispersions of the various components. In embodiments in which the article is supported, e.g., disposed on a fabric or other knitted liner or support material, the support material is disposed over the shaped former prior to disposing of the layers thereon.

[0049] In embodiments, the article is free from fluorinated polymers in the various layers. In embodiments, each of the layers are formed from colloids, which in embodiments is an aqueous latex, whichin embodiments is an aqueous latex-based colloidally stable rubber lattice. In embodiments, the outer elastomeric barrier layer is less than 50% by weight polyolefin, or less than 10% by weight polyolefin, or is essentially free of polyolefin.

[0050] In embodiments, an elastomeric article comprises an outer elastomeric barrier layer comprising NBR, chloroprene rubber, or a combination thereof, the outer elastomeric barrier layer bonded to a middle elastomeric layer comprising polyvinyl alcohol, the middle elastomeric layer bonded to an inner elastomeric skin-contact layer comprising a polyamide. In some embodiments, the outer elastomeric barrier layer is NBR, chloroprene rubber, or a combination thereof. In some embodiments, the middle elastomeric layer is polyvinyl alcohol. In some embodiments, the inner elastomeric skin-contact layer is a polyamide.

[0051] In embodiments, the inner elastomeric skin-contact layer comprises nylon 6, nylon 66, nylon 69, nylon 610, nylon 612, or a combination thereof. In some of such embodiments, the inner elastomeric skin-contact layer comprises: about 30 to about 75% by weight nylon 6; about 5 to about 80% by weight nylon 66; about 20 to about 55% by weight nylon 69; about 10 to about 80% by weight nylon 610; or about 10 to about 80% by weight nylon 612. In some of such embodiments, the inner elastomeric skin-contact layer comprises: i) a terpolymer comprising nylon 6, nylon 66, and nylon 69, wherein: the nylon 6 is present at about 35 to about 55% by weight; the nylon 66 is present at about 5 to about 35% by weight; and the nylon 69 is present at about 20 to about 55% by weight in the terpolymer; a terpolymer comprising nylon 6, nylon 66, and nylon 610, wherein: the nylon 6 is present at about 35 to about 75% by weight; the nylon 66 is present at about 10 to about 80% by weight; and the nylon 610 is present at about 10 to about 80% by weight in the terpolymer; or ill) a terpolymer comprising nylon 6, nylon 66, and nylon 612, wherein: the nylon 6 is present at about 30 to about 75% by weight; the nylon 66 is present at about 10 to about 80% by weight; and the nylon 612 is present at about 10 to about 80% by weight in the terpolymer.

[0052] In embodiments, the outer elastomeric barrier layer is from about 5 mils (0.13 mm) to about 20 mils (0.51 mm)in thickness, wherein the middle elastomeric layer is from about 0.3 mil (0.07 mm) to about 10 mils (0.25 mm) in thickness, and wherein the inner elastomeric skin-contact layer is from about 0.1 mils (0.003 mm) to about 5 mils (0.13 mm) in thickness. In embodiments, the elastomeric article has a maximum total thickness from about 6 mil (0.15 mm) to 35 mil (0.89 mm), which in other embodiments is less than or equal to about 24 mils (0.61 mm).

[0053] In some of such embodiments, the elastomeric article is a single use glove. In some embodiments, at least a portion of the inner elastomeric skin-contact layer is disposed over a woven or nonwoven support. In some embodiments, the elastomeric article is an industrial use glove.

[0054] In some of embodiments, two or more of the outer elastomeric barrier layer, the middle elastomeric layer, and the inner elastomeric skin-contact layer are cured simultaneously.

[0055] In some embodiments, the outer elastomeric barrier layer provides greater than about 50% of a thickness of the article.

[0056] In some embodiments, the elastomeric article is effective to provide a chemical permeation time in excess of 400 minutes pursuant to EN 16523-1:2015 for benchmark solvents of dichloromethane, toluene and tetrahydrofuran. In some embodiments, the elastomeric article has a permeation time measured pursuant to EN 16523-1 : 2015 and compared to a comparative for permeation time measured pursuant to EN 16523-1 : 2015 of a comparative elastomeric article having an outer elastomeric barrier layer free of NBR and chloroprene of the same thickness as the elastomeric article, the elastomeric article is effective to provide a dichloromethane chemical permeation time, an acetone permeation time, an ethyl acetate permeation time, and a methanol permeation time which is greater than the comparative permeation time for the comparative elastomeric article, wherein at least one permeation time is about five-times or greater than the corresponding comparative permeation time.Outer Elastomeric Barrier Laver

[0057] The outer elastomeric barrier layer can comprise a layer or sublayer of natural and synthetic lattices such as natural rubber (NR), chloroprene rubber (CR), butyl rubber (HR), acrylonitrile butadiene rubber (NBR or nitrile, which can be carboxylated), isoprene rubber (IR), styrene-butadiene rubber (SBR), polyurethane, Butyl and Viton rubber, combinations, and mixtures or blends thereof. In embodiments, the outer elastomeric barrier layer comprises a blend of the foregoing materials, with an elastomeric latex, thermoplastic saturated water dispersible polyester resin, ultrafine high molecular weight polyamide powder, ethylene based copolymers such as ethylene-propylene diene (EPDM) latex or styrene ethylene butylene styrene block copolymers (SEBS copolymers), hydrophobic type natural wax such as carnauba wax, and mixtures thereof. (In this context, "ultrafine" means average particle size of 20 microns or less by laser scanning. In this context, "high molecular weight" means a melting point from about 115 °C to about 180°C.)

[0058] In embodiments, the outer elastomeric barrier layer is formed from an aqueous latex-based colloidally stable rubber lattice. In embodiments, the rubber lattice comprises natural rubber, chloroprene rubber (CR), butyl rubber, acrylonitrile butadiene rubber (NBR), styrene-butadiene rubber, polyurethane, polyisoprene rubber, polyvinyl chloride, polyvinyl alcohol, ethylene vinyl acetate, ethylene propylene diene monomer, chlorosulfonated polyethylene rubber or a combination thereof.

[0059] The outer elastomeric barrier layer from natural and synthetic rubber lattices may be chosen for its barrier properties to chemicals, as well as its user-friendly properties such as flexibility and elasticity. The outer elastomeric barrier layer polymer can be for example chosen from polar synthetic elastomer such as polychloroprene (neoprene) or carboxylated acrylonitrile butadiene (carboxylated nitrile rubber) or non-polar synthetic elastomer such carboxylated styrene butadiene, butyl rubber, isoprene or otherwise blends of the foregoing.

[0060] In embodiments, the outer elastomeric barrier layer or sublayer adjacent to the middle elastomeric layer comprises predominantly (more than 50% wt. among polymeric components) acrylonitrile butadiene rubber (NBR), or carboxylated acrylonitrile butadiene rubber.

[0061] In embodiments, the outer elastomeric barrier layer or sublayer adjacent to the middle elastomeric layer comprises predominantly (more than 50% wt. among polymeric components) chloroprene rubber. In embodiments, such a predominantly chloroprene rubber sublayer is adjacent to another elastomeric polymeric barrier sublayer with a distinct polymer composition.

[0062] Blends of rubber lattices with non-polar elastomeric latex, such as SBR (e.g., carboxylated) or polyisoprene rubber (PI) can enhance swelling degradation resistance and permeation time with respect to polar solvents. Such a blend can be useful in forming a barrier layer when the blend is homogenous colloidally stable and compatible, and the blend does not create two-phase separation and voids between two polymer interfaces. In embodiments, a lattice of predominantly NBR, CR or a mixture thereof is blended with SBR, PI, butyl or a mixture thereof.

[0063] Hydrophobic additives such as hydrophobic wax (such as carnauba wax and polyolefin waxes) in the outer elastomeric barrier layer or sublayer can enhance outside surface hydrophobicity and assist in shielding or wicking off the contacting solvents from the outside layer, thus reduces further the potential of solvent swelling or permeation.

[0064] In embodiments, the outer elastomeric barrier layer or sublayer comprises a thermoplastic polyester. By "thermoplastic," it is meant that the polymer, in another context, can be used to form hot melt compositions. The amounts by weight of elastomer to polyester can be for example from about 19: 1 by wt to about 4:6, or from about 9:1 to about 7:3, or about 5 % to about 30 % by wt. Such blends enhance resistance to solvent swelling and / or permeation.

[0065] FIG. 2 shows an idealized version of such a polyester. Note the positions of the ester groups( - c - o - C) and the reactive sites (-C*=C*-) within the molecular chain. In embodiments, the weight average molecular weight Mw of the polyester is from about 14,000 to about 26,000 g / mol.

[0066] The polyester is usefully hydrophobic, meaning that it resists water, resulting in minimal water being absorbed by it. The polyester usefully also dries quickly and shows a "wicking effect." Thus, by introducing a hydrophobic polyester, which can be saturated, in the outer elastomeric barrier layer on the outside of the article, solvents in contact with that layer can be wick away and reduce the potential of solvents swelling and degradation. Moreover, a number of lattices such as nitrile or neoprene lack of resistance to polar solvents such as acetone or toluene, and these polymers are shielded by the presence of hydrophobicpolyester in the first layer of elastomer / polyester blends. (By "saturated" it is meant that any remaining unsaturation is low and not enough to provide effective crosslinking.)

[0067] In other variants, the outer elastomeric barrier layer can also be blended with water dispersible non-polar thermoplastics such as saturated water dispersible polyester resin, for example having a softening point above 50 °C. Such Thermoplastic elastomer compositions exhibit exceptional resistance to solvent swelling. The polyester is advantageously a linear polyester such as terephthalate, isophthalate or copolyester thereof, e.g., polyethylene terephthalate (PET) and polytetramethylene terephthalate (PBT).

[0068] In embodiments, the outer elastomeric barrier layer 10 can be blended with for example 5 -20 % ultrafine high performance polyamide powder such as Orgasol PA12® (Arkena Global, France), and / or 1 - 5 % acid anhydride modified polyolefin, and / or 1 - 5 % fatty acid amide soap, and / or mixtures thereof. The polymer composition, such as a blended mixture, can also be enhanced with water soluble carbodiimide compounds such as Zoldine XL-29SE® (Advancion, USA) crosslinker and / or high acid ionomer of ethylene and methacrylic acid copolymer resins such as Surlyn® and Nucrel® (Dow, USA). Such acid anhydride-modified polyolefin polymer can be combined with a polyamide powder polymer and / or fatty acid amide soap to form a non-ionomeric composition and linked to the carboxylated nitrile polymer by the dehydration reactions mediated by the carbodiimide compounds. The acid anhydride-modified polyolefin polymers include, for example ethylene-based copolymers, particularly ethylene-propylene (EP) ethylene-butene (EB); ethylene-hexene (EH); ethylene-octene; styrene-ethylene / butylene-styrene (SEBS), ethylene-propylene diene (EPDM), ethylene-vinyl acetate (EVA) and various ethylene-alkyl acrylate copolymers such as, for example, ethylene-methyl acrylate (EMA); ethylene-ethyl acrylate (EEA) and various ethylene-propyl acrylate (EPA); ethylene-butyl acrylate (EBA) copolymers; and the like.

[0069] Other polyolefin-based copolymers also can be used such as polypropylene and polybutene-based copolymers. These copolymers include random, block, and graft copolymers which have been functionalized with acid anhydride groups. Examples of commercially available acid anhydride polyolefin that can be used include, but not limited to, Amplify GR® functional polymers (DOW, USA), Fusabond® polymers (DOW, USA), Polybond® (Polybond, USA) and Royaltuft® (Akrochem Corp. USA).

[0070] In embodiments, the polymer of the outer elastomeric barrier layer further comprises vinyl polymers comprising oxo or carbonyl (-(C=O)-) groups or moieties.

[0071] In embodiments the polymer of the outer elastomeric barrier layer is primarily not polyolefin (i.e., <50% wt of polymers). In embodiments the polymer of the outer elastomeric barrier layer is substantially not polyolefin (<30%). In embodiments the polymer of the outer elastomeric barrier layer is materially not polyolefin (<20%). In embodiments the polymer of the outer elastomeric barrier layer is essentially not polyolefin (<5%).

[0072] In embodiments, an elastomeric article comprises an outer elastomeric barrier layer comprises, consists essentially or, or consists of (i.e., is) NBR, chloroprene rubber, or a combination thereof.Middle Elastomeric Laver

[0073] In embodiments, the middle elastomeric layer comprises polyvinyl alcohol, or a blend comprising polyvinyl alcohol and one or more of polyvinyl chloride, butyl rubber, ethylene propylene diene monomer (EPDM), chlorosulfonated polyethylene rubber (CSM), or a combination thereof, disposed by dipping the middle elastomeric layer on the outer elastomeric barrier layer.

[0074] In embodiments, the middle elastomeric layer comprises greater than or equal to about 50.1 wt% polyvinyl alcohol, or greater than or equal to about 60 wt% polyvinyl alcohol, or greater than or equal to about 70 wt% polyvinyl alcohol, or greater than or equal to about 80 wt% polyvinyl alcohol, or greater than or equal to about 90 wt% polyvinyl alcohol, or greater than or equal to about 95 wt% polyvinyl alcohol, or greater than or equal to about 99 wt% polyvinyl alcohol. In embodiments, the middle elastomeric layer consists essentially of polyvinyl alcohol. In embodiments, the middle elastomeric layer consists of (i.e., is) polyvinyl alcohol.

[0075] In embodiments, the middle elastomeric layer is a blend comprising polyvinyl alcohol and one or more elastomers present in the outer elastomeric barrier layer, one or more elastomers present in the inner elastomeric layer, or a combination thereof. In such embodiments, the blend may be formed at the interface between the outer elastomeric barrier layer and the middle elastomeric layer, and / or between the middle elastomeric layer and the inner elastomeric layer during the disposition of the various layers one on top of the other.

[0076] In embodiments in which the inner elastomeric layer comprises polyamide, without being limited to theory, the middle elastomeric layer is believed to form a strong hydrogen and polar bonds to the inner elastomeric layer. The result of this is believed to be markedly enhanced resistance to permeation and swelling by chlorinated and aromatic solvents. One measure of this is enhanced resistance to dichloromethane, to aromatic solvents, and to ethereal solvents, regardless of the face of the face of the laminate to which the solvent is applied. Other measures of enhanced resistance to permeation or swelling by polar solvents are described herein. These measures show that the middle elastomeric layer is effective, irrespective of whether Applicant's theory is correct.

[0077] In embodiments, in addition to the middle elastomeric layer comprising at least 50.1 wt% polyvinyl alcohol, the middle elastomeric layer may further include one more of ethylene vinyl acetate (EVA), ethylene methyl acrylate (EMA), acid modified olefin copolymers such as ethylene acrylic acid (EAA) or ethylene grafted maleic anhydride (AMP), ethylene vinyl polyester, ethylene vinyl chloride, polyethylene, polystyrene, or blends of two or more of the forgoing. In embodiments, the middle elastomeric layer is usedas a water-based dispersion, and is applied to the outer elastomeric barrier layer by dipping of the coated former into the water-based dispersion of the middle elastomeric layer.

[0078] The middle elastomeric layer can be for example a polyvinyl alcohol emulsion, which may further include a small amount of other materials as protective colloids. The middle elastomeric layer can be chosen for its elastomeric softness, chemical resistance, flexibility and its effectiveness as binder adhesive (e.g., a tie layer) to both synthetic latex and polyamide surfaces. Either carboxylated acrylonitrile-butadiene or polychloroprene or its blends is tied up with a layer of strong hydrogen bonding to the polyamides such as polycaprolactam (Nylon 6), polyhexamethyleneadipamide (Nylon 6,6) and poly hexamethylenesebecamide (Nylon 6,10).

[0079] Minor portions of polymers with compatibilizing effect with polyamide polymer and / or a strong barrier of hydrogen bonds against various polar solvents and esters can be added. Examples include polyacrylic acid, polyacrylamide, polyethylene, polystyrene, and mixtures thereof. In embodiments, such polymers are present during the polymerization of the middle elastomeric layer and can act either as colloidal stabilizer, adhesion promoter or crosslinker in a water-based emulsion polymerization process.

[0080] In embodiments, the polyvinyl alcohol has a hydrolysis level of greater than or equal to about 80%, or greater than or equal to about 90%, or greater than or equal to about 95%, or greater than or equal to about 99%, i.e., fully hydrolyzed.

[0081] In embodiments, the polyvinyl alcohol has a degree of polymerization of greater than or equal to about 150, or greater than or equal to about 350, or greater than or equal to about 1000, or greater than or equal to about 1600.

[0082] In embodiments, the polyvinyl alcohol has weight average molecular weight (Mw) from about 13,000 to 23,000 g / mol, or from about 31,000 to 50,000 g / mol, or from about 85,000 to 124,000 g / mol, or from about 146,000 to 186,000 g / mol.

[0083] In embodiments, the middle elastomeric layer comprises, consists essentially of, or consists of (i.e., is) polyvinyl alcohol.Inner Elastomeric Laver

[0084] The inner elastomeric layer, which in embodiments is the inner elastomeric skin-contact layer, can be formed of any number of elastomeric and / or polymeric materials, and may include any materials present in the outer elastomeric barrier layer and / or, the middle elastomeric layer. In embodiments, the inner elastomeric layer comprises one or more of acrylic polymer, polyurethane, natural rubber, chloroprene rubber, butyl rubber, acrylonitrile butadiene rubber, styrene-butadiene rubber, polyurethane, polyisoprene rubber, polyvinyl chloride, polyvinyl alcohol, ethylene vinyl acetate, ethylene propylene diene monomer, chlorosulfonated polyethylene rubber, or a combination thereof.

[0085] In embodiments, the inner elastomeric layer comprises a polyamide material, including those described below orthose built from the building blocks described below. It is believed that binary, tertiary or further blends of polyamides can enhance solvent resistance.

[0086] In embodiments, the inner elastomeric layer is disposed on the middle elastomeric layer by dipping, and comprises a polyamide polymer, which may be a blend of polyamide polymers, or a blend comprising one or more polyamide polymers and one or more of acrylic polymer, polyurethane, natural rubber, chloroprene rubber, butyl rubber, acrylonitrile butadiene rubber, styrene-butadiene rubber, polyurethane, polyisoprene rubber, polyvinyl chloride, polyvinyl alcohol, ethylene vinyl acetate, ethylene propylene diene monomer, chlorosulfonated polyethylene rubber, or a combination thereof.

[0087] The polyamide or polyamides can be chosen from either nylon terpolymer solution prepared from a selected monomer groups of epsilon caprolactam or 2-oxohexamethyleneimine, polymethylene diamine and polymethylene diacides including prepared by condensing a monocarboxylic acid, diamine and dimerized fatty acid, condensing an acid component of dimerized fatty acids, at least one aliphatic unbranched monocarboxylic acid and at least one aliphatic branched monocarboxylic acid with ethylene diamine and hexamethylene diamine as the amine component. A particular useful class of polyamides includes those in which (a) about 98-100 mole percent of the imine groups are derived from hexamethylene diamine, (b) about 15-55 %, and preferably about 25-55, mole percent of the carbonyl groups are derived from dimerized fatty acid of 36 carbon atoms, (c) about 10-45, and preferably about 5-45, mole percent of the carbonyl groups are derived from polymethylene diacid of 10-20 carbon atoms.

[0088] Usefully, these polyamides can have a minimum flow temperature of about 100 to about 2000C. Suitable polymethylene diamines for preparing suitable polyamides include hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecamethylene diamine, and octadecamethylene diamines. Suitable polymethylene diacids for preparing suitable polyamides include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic, brassilic, tetradecandioic, octadecanedioic, and 1,10-decanedicarboxylic acid. Suitable aminoacids include 6-aminocaproic, 7-aminoheptanoic, 8-aminocaprylic, 9-aminononanoic, 10-aminodecanoic, 11-aminoundecanoic, 17-aminoheptadecanoic, and the like. The polyamide can be blends of polyamide and copolyamides block copolymers and graft copolymer solution. Useful polymers derived from the polyamides preparation includes nylons selected from a mixture consisting of one, two or three of nylon 6, nylon 66, nylon 69, nylon 610 and nylon 612.

[0089] The inner elastomeric layer for example can be chosen from resins with lower melting ranges starting preferably from 100 to 200 degrees Celsius. Commercially available nylons having a softening point above 100 °C can be advantageously used in the practice of embodiments disclosed herein. Examples of suitable polyamides are various Nylons® (Dupont, USA), which include polylactams (Nylon 6),polypropiolactam (Nylon 3), polyenantholactam (Nylon 7), polycaprylactam (Nylon 8), polylaurylactam (Nylon 12), and the like; homopolymers of amino acids such as polyaminoundecanoic acid (Nylon 11); polypyrrolidinone (Nylon 4); copolyamides of dicarboxylic acid and diamine such as Nylon 6,6, polytetramethyleneadipamide (Nylon 4,2), polyhexamethylenesebacamide (Nylon 6.10), polyhexamethyleneisophhthlamide (Nylon 6.1), polyhexamethylenedodecanoic acid (Nylon 6.12) and the like; aromatic and partially aromatic polyamides; copolyamides such as of caprolactam and hexamethyleneadipamide (Nylon 6 / 6.6) or a terpolyamide e.g. Nylon 6 / 6.6 / 6.10; block copolymers such polyether polyamide; or mixtures thereof. A terpolymer mix of a certain composition ratio can be particularly useful.

[0090] A useful range of nylon terpolymer composition mix is Nylon 6 / 66 / 69 at 35-55% / 5-35 % / 20-55 %. Another useful range of Nylon Terpolymer composition mix at Nylon 6 / 66 / 610 at 30-75% / 10-80 % / 10-80 %. Alternatively, another useful range of Nylon Terpolymer composition mix is Nylon 6 / 66 / 612 at 30-75 % / 10-80 % / 10-80 %. [All ranges or amounts from about to about.]

[0091] In embodiments, the inner elastomeric layer comprises primarily (by weight) polyamides among polymer components.

[0092] In embodiments, the inner elastomeric layer is the skin-contact layer, and comprises, consists essentially of, or consists of (i.e., is) a polyamide.

[0093] In applying the inner elastomeric layer to the middle elastomeric layer, the polyamide can be dispersed in water, or in solvent such as ethanol, methanol, 2-propanol, 1 -propanol, 1 -butanol, benzyl alcohol, furfuryl alcohol, formic acid, phenol, m-cresol and the like, and / or mixtures of these or mixtures thereof with water.

[0094] Exemplary nylons include:<Features of the Laminate of Lavers 10, 12 and 14

[0095] As compared to the barrier properties of any prior art, as has been demonstrated experimentally, the materials of embodiments make it possible to increase the time taken for the solvents to pass through an article of the laminate, and to constitute a barrier across a broad expanded range ofchemicals. That range never having been achieved in the past with primary elastomeric polymers such as nitrile, neoprene or butyl. Moreover, this material have good elasticity, less bulky and less plastic feel as compared to other prior arts using welded HDPE plastic and / or HDPE bonded as an inner lining to a butyl glove. Such HDPE gloves have a wide range of chemical resistance, but have a plastic feel and are baggy in the palm area. Thus, these gloves provide the user with less dexterity and comfort.Coating Laver, Donning Laver; Other internal layers

[0096] Subsequent layers (Layer 8 and / or Layer 16), such as a coating layer or a donning layer, can use any polymeric adhesive for donning materials such as acrylates, polyurethane, any other synthetic lattices and / or off line thermal hot melts adhesive bonding of knitted liners made from fabric such as fabrics of cotton, nylon, HPPE, Kevlar, like materials, and combinations. In embodiments, the coating layer comprises natural rubber, chloroprene rubber, butyl rubber, acrylonitrile butadiene rubber, styrene-butadiene rubber, polyurethane, polyisoprene rubber, polyvinyl chloride, polyvinyl alcohol, ethylene vinyl acetate, ethylene propylene diene monomer, chlorosulfonated polyethylene rubber, or a combination thereof. In embodiments, the coating layer comprises acrylonitrile butadiene rubber.

[0097] In embodiments, the coating layer or subsequent layers may be applied to the former prior to the other layers being disposed over the former, or the coating layer or subsequent layers may be applied to article prior to removing the article from the former. In other embodiments, the coating layer or subsequent layers may be applied to the article after being removed from the former.Exemplary Process of Making

[0098] In FIG. 3, process 20 can begin with block 22, applying a coagulant to a shaped former, also referred to as a mandrel. Where the disposition block 24 when present, or 26 does not need a coagulant, block 22 can be omitted. In block 22, the coagulant (if applied) is dried.

[0099] In block 24, a coating layer 8 is disposed onto the mandrel. The coating layer 8 may be dried. In block 26, the material of the outer elastomeric barrier layer 10 is disposed over the mandrel. In embodiments, Layer 10 is applied by dipping. If multiple layers which form Layer 10 are applied, these can be by dipping, spraying, and or the like, and are typically followed by drying. After disposition of layer 10, the mandrel can be turned over or otherwise manipulated to control drip. In block 28, the applied polymer can be leached (optional). The mandrel can be turned over or otherwise manipulated to control drip. In block 30, the applied material can be dried. In embodiments, the layer 10 material is cured prior to proceeding with further blocks, and a cure block can be omitted later. For example, curing may substitute for block 30, or follow block 30 (prior to block 32). In other embodiments, two or more of the layer 10, layer 12, and layer 14 are applied, and the and the applied layers are cured simultaneously, thereby increasing intralayer bonding.

[0100] In block 32, the middle elastomeric layer 12 is applied, typically by spaying and / or dipping. The mandrel can be turned over or otherwise manipulated to control drip, and then dried in block 34. In block 36, the inner elastomeric layer 14 material can be applied, typically by dipping. The mandrel can be turned over or otherwise manipulated to control drip. In block 40, the applied material can be dried. In embodiments, block 36, or blocks 36 and 40, are repeated.

[0101] In optional block 42, donning or coating materials, such as nitrile rubber, polyacrylates, or polyurethanes are applied. In an embodiment, Adhesive is applied (block 42A) and then flock is applied (block 42B).

[0102] In embodiments, a hot melt adhesive is applied to allow the stripped article to be adhered to a fabric liner. For example, a stripped glove with layer 14 on the outside (after reinversion from stripping) is mounted on a collapsible mandrel, a hot melt thermoplastic glue is then applied before a liner is fabricated onto the glued glove followed for example by air inflation and hot melt oven drying.

[0103] In block 44, if the polymers used need curing, they are cured. The article can be stripped from the mandrel (block 46) e.g., via inversion. After drying or curing blocks, the mandrel can be cooled.

[0104] In embodiments, a hot melt adhesive is applied to allow the stripped article to be adhered to a fabric liner. For example, a stripped glove with layer 14 on the outside (after reinversion from stripping) is mounted on a collapsible mandrel, a hot melt thermoplastic glue is then applied before a liner is fabricated onto the glued glove followed by air inflation and hot melt oven drying.

[0105] Another variant is by applying Layer 12 before curing and dipping into Layer 14 after curing. In such variant, there curing may substitute for block 34, or follow block 34. Other process blocks can remain unchanged.

[0106] In embodiments, the method of forming the elastomeric article comprises disposing the inner elastomeric layer over a shaped former; disposing the middle elastomeric layer onto the inner elastomeric layer; disposing the outer elastomeric barrier layer onto the middle elastomeric layer to form the elastomeric article; and removing the elastomeric article from the shaped former. In such embodiments, the elastomeric article is not inverted during removal from the shaped former.

[0107] In some embodiments, at least a portion of the inner elastomeric layer is disposed over a woven or non-woven support. Accordingly, in some embodiments, the method further comprises disposing a woven or non-woven support over the shaped former prior to disposing the inner elastomeric layer over the shaped former. In embodiments, a woven support is formed directly on the shaped former.

[0108] In embodiments, the elastomeric article is a single use glove. In some embodiments, wherein the inner elastomeric layer comprises polyamide, the elastomeric article is an industrial use glove.

[0109] However, in other embodiments, the elastomeric article is an article of protective clothing, referred to herein generically as a “coverall”, or a portion of a coverall. For purposes herein, a “coverall” ora portion of a coverall includes, but is not limited to: jumpsuits, bodysuits, aprons, gowns, shoe covers, leggings, bibs, head covers, and the like, which are configured to be donned over a portion of a human (or the entire human being) at risk of chemical or other environmental exposure with the article, wherein wearing of the article for a period of time during which there is a risk of such exposure reduces or eliminates the exposure of the portion of the human to chemical or other environmental exposure.Permeation Resistances

[0110] In embodiments, the elastomeric article provides certain minimal permeation times as measured by EN 16523-1:2015. Six new chemicals have been added to the list of hazardous compounds under the condition of continuous contact from original specified 12 chemicals in EN 374-3. One pictogram and three types of gloves are specified; Type A with breakthrough time > or = 30 min for at least 6 chemicals; Type B with breakthrough time > or = 30 min for at least 3 chemicals; Type C with breakthrough time > or = 10 min for at least 1 chemical in the new list. The test method is applicable to the assessment of protection against liquid chemicals that can be collected only by liquid or gaseous collecting media, is not adapted for the assessment of chemical mixtures, except for aqueous solutions, is used for gloves with the following information defined: a preconditioning of sample for at least 16 h at a temperature of 23 + / - 2 deg C and assembled permeation cell placed in a temperature controlled room at similar temperature. For multilayer protective clothing or glove material, in case of unbonded layers (in this case not applicable to embodiments where liner is thermally hot melt bonded), the internal layers without any effect on the chemical protection can be removed (e.g., thermal insulation layers). The final measurement is the average of three individual specimen per glove for a total of 3 gloves of each lot of chemical barriers.

[0111] In embodiments, permeation times for one or more of dichloromethane, toluene, and / or tetrahydrofuran, are 400 minutes or more, resulting in a level 5 or level 6 rating according to ENISO16-523. In embodiments, permeation times for one or more of acetone, acetonitrile, ethyl acetate, methylethylketone, methyisobutylketone, diethylamine, methanol or ethanol are 30 minutes or more, or 50 minutes or more, or 100 minutes or more, or 200 minutes or more, or 300 minutes or more, or 400 minutes or more, or 480 minutes or more. In embodiments, permeation times for sulfuric acid are 30 minutes or more, or 50 minutes or more, or 100 minutes or more.

[0112] Coating thicknesses, uniformity or evenness, moisture or air traps (voids), dryness between each layer, dryness of the leached glove before and after application of the middle elastomeric layer, are important process variables

[0113] In embodiments one or more of the above permeation time values pertain if the material is applied to the layer 14 side (second side) or the layer 10 side (first side). For one or more of the remainingchemicals recited in the paragraph above, in embodiments one or more of the above values pertain if applied to the layer 10 side (first side).Degradation Resistance

[0114] In embodiments, the elastomeric article provides certain maximal degradation percentages (swelling) as measured by EN 374-4:2013. The principle of this testing is to measure if there is a change in the force required to puncture the glove material after continuous contact of its external surface with a challenge chemical for 1 hour continuous exposure to the challenge chemical. This puncture test is very similar to the procedure detailed in the performance standard to assess protection from mechanical risks detailed in EN 388:2016. The force required to push a standard stylus through a sample of the glove material is compared before and after exposure to the challenge chemical for 1 hour continuous period. The final measurement is the average of three individual measurements for a given lot of chemical barriers. In embodiments, for one or more of toluene, ethyl acetate (EtOAc), acetone, MeOH or sulfuric acid, the value can be about 30% or less. In embodiments, for one or more of EtAc, acetone, MeOH or sulfuric acid, the value can be about 20% or less. In embodiments, for one or more of EtAc or sulfuric acid, the value can be about 15% or less.Flexibilitv / Stiffness

[0115] In embodiments the gloves have stiffness of 130, or 125, or 123.4 mgf or less, as measured by a Gurley stiffness Tester (Model 4171T, Gurley Precision Instruments, Troy, NY). In comparison, the invented elastomeric article, in this case a glove, is comparable to a typical bonded butyl glove (MAPA Butoflex 650, MAPA Professional) apart from bonded Neoprene (Nitopren 717, Honeywell Safety, Basingstoke, UK), the invented glove is more flexible (less stiff) than bonded Neoprene (Scorpio 08-354, Ansell, Iselin, NJ), bonded Nitrile (Flexiproof, Ansell) and bonded PVC (Multiplus, Ansell). Values as an average of four sets of data were:

[0116] Described herein is an elastomeric article, principally a glove, having a chemical barrier and methods of forming and using the same. Although some embodiments have been discussed above, other implementations and applications are also within the scope of the following claims. Although the instant disclosure describes particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of this disclosure. It is therefore to be understood that numerousmodifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and scope of the present disclosure, as defined by the following claims. More specifically, those of skill will recognize that any embodiment described herein that those of skill would recognize could advantageously have a sub-feature of another embodiment, is described as having that subfeature

[0117] Publications and references, including but not limited to patents and patent applications, cited in this specification are herein incorporated by reference in their entirety in the entire portion cited as if each individual publication or reference were specifically and individually indicated to be incorporated by reference herein as being fully set forth. Any patent application to which this application claims priority is also incorporated by reference herein in the manner described above for publications and references.

Claims

What is claimed is:

1. An elastomeric article comprising an outer elastomeric barrier layer bonded to a middle elastomeric layer comprising polyvinyl alcohol, which is bonded to an inner elastomeric layer.

2. The elastomeric article of claim 1, wherein the middle elastomeric layer is a blend comprising polyvinyl alcohol and one or more elastomers present in the outer elastomeric barrier layer, one or more elastomers present in the inner elastomeric layer, or a combination thereof.

3. The elastomeric article of any one of claim 1 or claim 2, wherein the outer elastomeric barrier layer is formed from an aqueous latex-based colloidally stable rubber lattice comprising natural rubber, chloroprene rubber, butyl rubber, acrylonitrile butadiene rubber, styrene-butadiene rubber, polyurethane, polyisoprene rubber, polyvinyl chloride, polyvinyl alcohol, ethylene vinyl acetate, ethylene propylene diene monomer, chlorosulfonated polyethylene rubber or a combination thereof.

4. The elastomeric article of any one of claims 1 through 3, wherein polymers of the outer elastomeric barrier layer comprise greater than 50% by weight butyl, NBR, chloroprene, or blends thereof, and further comprises vinyl polymers comprising oxo (-(C=O)-) groups, each comprising a carbon atom doubled bonded to an oxygen atom.

5. The elastomeric article of any one of claims 1 through 4, wherein the outer elastomeric barrier layer is essentially free of polyolefin.

6. The elastomeric article of any one of claims 1 through 5, wherein polymers of the outer elastomeric barrier layer are blended with a water dispersible saturated polyester resin, ultrafine high molecular weight polyamide powder, ethylene based copolymer, a hydrophobic wax, or a mixture thereof.

7. The elastomeric article of any one of claims 1 through 6, wherein the outer elastomeric barrier layer is from about 5 mils to about 20 mils in thickness, wherein the middle elastomeric layer is from about 0.3 mil to about 10 mils in thickness, and wherein the inner elastomeric layer is from about 0.1 mils to about 5 mils in thickness.

8. The elastomeric article of any one of claims 1 through 7, having a maximum total thickness of less than or equal to about 24 mils (0.61 mm).

9. The elastomeric article of any one of claims 1 through 8, wherein the outer elastomeric barrier layer comprises a blend of EPDM and neoprene rubber;wherein the middle elastomeric layer comprises polyvinyl alcohol or a blend comprising polyvinyl alcohol and one or more of polyvinyl chloride, butyl rubber, ethylene propylene diene monomer (EPDM), chlorosulfonated polyethylene rubber (CSM), or a combination thereof; andwherein the inner elastomeric layer comprises polyamide polymer; or a blend comprising polyamide polymer and one or more of acrylic polymer, polyurethane, natural rubber, chloroprene rubber, butyl rubber, acrylonitrile butadiene rubber, styrene-butadiene rubber, polyurethane, polyisoprene rubber, polyvinyl chloride, polyvinyl alcohol, ethylene vinyl acetate, ethylene propylene diene monomer, chlorosulfonated polyethylene rubber, or a combination thereof.

10. The elastomeric article of any one of claims 1 through 9, wherein the middle elastomeric layer further comprises polyethylene, polystyrene, EVA, EMA, EAA, ethylene vinyl polyester, ethylene grafted maleic anhydride, AMP, or mixtures thereof.

11. The elastomeric article of any one of claims 1 through 10, wherein the outer elastomeric barrier layer comprises NBR and a water dispersible polyester resin.

12. The elastomeric article of any one of claims 1 through 11, wherein the inner elastomeric layer comprises nylon 6, nylon 66, nylon 69, nylon 610, nylon 612, or a combination thereof.

13. The elastomeric article of any one of claims 1 through 12, wherein the inner elastomeric layer comprises:about 30 to about 75% by weight nylon 6;about 5 to about 80% by weight nylon 66;about 20 to about 55% by weight nylon 69;about 10 to about 80% by weight nylon 610; orabout 10 to about 80% by weight nylon 612.

14. The elastomeric article of any one of claims 1 through 13, wherein the inner elastomeric layer comprises:i) a terpolymer comprising nylon 6, nylon 66, and nylon 69, wherein:the nylon 6 is present at about 35 to about 55% by weight;the nylon 66 is present at about 5 to about 35% by weight; andthe nylon 69 is present at about 20 to about 55% by weight in the terpolymer;ii) a terpolymer comprising nylon 6, nylon 66, and nylon 610, wherein:the nylon 6 is present at about 35 to about 75% by weight;the nylon 66 is present at about 10 to about 80% by weight; andthe nylon 610 is present at about 10 to about 80% by weight in the terpolymer; oriii) a terpolymer comprising nylon 6, nylon 66, and nylon 612, wherein:the nylon 6 is present at about 30 to about 75% by weight;the nylon 66 is present at about 10 to about 80% by weight; andthe nylon 612 is present at about 10 to about 80% by weight in the terpolymer.

15. The elastomeric article of any one of claims 1 through 14, wherein the outer elastomeric barrier layer comprises chloroprene and hydrophobic wax, and wherein the middle elastomeric layer further comprises EVA copolymer.

16. The elastomeric article of any one of claims 1 through 15, wherein the outer elastomeric layer comprises less than about 30% by weight of a polyolefin.

17. The elastomeric article of any one of claims 1 through 16, wherein the inner elastomeric layer comprises one or more polymers formed from monomers selected from the group consisting of caprolactam, adipic acid, azelaic acid, sebacic acid, 1 ,10-decanedicarboxylic acid and hexamethylene diamine.

18. The elastomeric article of any one of claims 1 through 17, wherein the outer elastomeric barrier layer provides greater than about 50% of a thickness of the article.

19. The elastomeric article of any one of claims 1 through 18, further comprising a coating layer having a thickness of less than or equal to about 5 mils (0.13mm) disposed over the outer elastomeric barrier layer, the inner elastomeric layer, or both.

20. The elastomeric article of claim 19, wherein the coating layer comprises natural rubber, chloroprene rubber, butyl rubber, acrylonitrile butadiene rubber, styrene-butadiene rubber, polyurethane, polyisoprene rubber, polyvinyl chloride, polyvinyl alcohol, ethylene vinyl acetate, ethylene propylene diene monomer, chlorosulfonated polyethylene rubber, or a combination thereof.

21. The elastomeric article of any one of claims 1 through 20, wherein at least a portion of the inner elastomeric layer is disposed over a woven or non-woven support.

22. An elastomeric article having a layered structure comprising:an outer elastomeric barrier layer bonded to a middle elastomeric layer comprising polyvinyl alcohol, which is bonded to an inner elastomeric layer,wherein the outer elastomeric barrier layer is formed from an aqueous latex-based colloidally stable rubber lattice comprising natural rubber, chloroprene rubber, butyl rubber, acrylonitrile butadiene rubber, styrene-butadiene rubber, polyurethane, polyisoprene rubber, polyvinyl chloride, polyvinyl alcohol, ethylene vinyl acetate, ethylene propylene diene monomer, chlorosulfonated polyethylene rubber or a combination thereof;wherein the middle elastomeric layer comprises polyvinyl alcohol, or a blend comprising polyvinyl alcohol and one or more of polyvinyl chloride, butyl rubber, ethylene propylene diene monomer (EPDM), chlorosulfonated polyethylene rubber (CSM), or a combination thereof;wherein the inner elastomeric layer comprises polyamide polymer, or a blend comprising polyamide polymer and one or more of acrylic polymer, polyurethane, natural rubber, chloroprene rubber, butyl rubber, acrylonitrile butadiene rubber, styrene-butadiene rubber, polyurethane, polyisoprene rubber, polyvinyl chloride, polyvinyl alcohol, ethylene vinyl acetate, ethylene propylene diene monomer, chlorosulfonated polyethylene rubber, or a combination thereof; andwherein one or more of the layers are disposed by dipping and one or more of the layers are dried and cured after said dipping.

23. The elastomeric article according to claim 22, wherein the aqueous latex-based colloidally stable rubber lattice comprises greater than about 50% by weight of the rubber lattice blended in an aqueous elastomeric latex, the rubber lattice comprising natural rubber, chloroprene rubber, butyl rubber, acrylonitrile butadiene rubber, styrene-butadiene rubber, polyurethane, or a combination thereof.

24. The elastomeric article of any one of claims 22 through 23, wherein the middle elastomeric layer comprises greater than or equal to about 50.5 % by weight polyvinyl alcohol.

25. The elastomeric article of any one of claims 22 through 24, wherein two or more of the outer elastomeric barrier layer, the middle elastomeric layer, and the inner elastomeric layer are cured simultaneously.

26. The elastomeric article of any one of claims 22 through 25, wherein the outer elastomeric barrier layer is less than 50% by weight polyolefin.

27. The elastomeric article of any one of claims 22 through 26, wherein the outer elastomeric barrier layer provides greater than about 50% of a thickness of the article.

28. The elastomeric article of any one of claims 22 through 27, wherein the layered structure is effective to provide a chemical permeation time in excess of 400 minutes pursuant to EN 16523-1 :2015 for benchmark solvents of dichloromethane, toluene and tetrahydrofuran.

29. The elastomeric article of any one of claims 22 through 28, wherein, for permeation time measured pursuant to EN 16523-1:2015 and compared to a comparative layer of material of the outer elastomeric barrier layer different than the outer elastomeric barrier layer, of a thickness of the layered structure, the layered structure is effective to provide a dichloromethane chemical permeation time, an acetone permeation time, an ethyl acetate permeation time, and a methanol permeation time which is greater than a corresponding permeation time for the comparative layer, wherein at least one permeation time is about five-times or greater than the corresponding permeation time of the comparative layer.

30. The elastomeric article of any one of claims 1 through 29, wherein the elastomeric article is a single use glove.

31. The elastomeric article of any one of claims 1 through 29, wherein the elastomeric article is a coverall, or a portion of a coverall.

32. The elastomeric article of any one of claims 1 through 29, wherein the inner elastomeric layer comprises polyamide, and wherein the elastomeric article is an industrial use glove.

33. A method of forming an elastomeric article according to any one of claims 1 through 32, comprising:disposing the outer elastomeric barrier layer over a shaped former;disposing the middle elastomeric layer onto the outer elastomeric barrier layer;disposing the inner elastomeric layer onto the middle elastomeric layer to form the elastomeric article; andremoving the elastomeric article from the shaped former by inversion.

34. The method of claim 33, further comprising disposing a coating layer over the shaped former prior to disposing the outer elastomeric barrier layer coating onto the shaped former.

35. The method of claims 33 or 34, further comprising disposing a coating layer over the inner elastomeric layer prior to removing the elastomeric article from the shaped former by inversion.

36. The method of any one of claims 33 through 35, wherein at least one of the outer elastomeric barrier layer, the middle elastomeric layer, and the inner elastomeric layer are disposed by dipping.

37. The method of any one of claims 33 through 36, wherein two or more of the outer elastomeric barrier layer, the middle elastomeric layer, and the inner elastomeric layer are disposed prior to curing the two or more layers simultaneously.

38. A method of forming an elastomeric article according to any one of claims 1 through 32, comprising:disposing the inner elastomeric layer over a shaped former;disposing the middle elastomeric layer onto the inner elastomeric layer;disposing the outer elastomeric barrier layer onto the middle elastomeric layer to form the elastomeric article; andremoving the elastomeric article from the shaped former.

39. The method of claim 38, further comprising disposing a coating layer over the shaped former prior to disposing the inner elastomeric layer over the shaped former.

40. The method of claim 38 or 39, further comprising disposing a coating layer over the outer elastomeric barrier layer prior to removing the elastomeric article from the shaped former.

41. The method of any one of claims 38 through 40, further comprising disposing a woven or non-woven support over the shaped former prior to disposing the inner elastomeric layer over the shaped former.

42. The method of any one of claims 38 through 41 , wherein at least one of the outer elastomeric barrier layer, the middle elastomeric layer, and the inner elastomeric layer are disposed by dipping.

43. The method of any one of claims 38 through 42, wherein two or more of the outer elastomeric barrier layer, the middle elastomeric layer, and the inner elastomeric layer are disposed prior to curing the two or more layers simultaneously.

44. A method of using the elastomeric article according to any one of claims 1 through 32, comprising:donning a portion of a human at risk of chemical exposure with the article; and wearing the article for a period of time during which there is a risk of such exposure.

45. An elastomeric article comprising an outer elastomeric barrier layer comprising NBR, chloroprene rubber, or a combination thereof, the outer elastomeric barrier layer bonded to a middle elastomeric layer comprising polyvinyl alcohol, the middle elastomeric layer bonded to an inner elastomeric skin-contact layer comprising a polyamide.

46. The elastomeric article of claim 45, wherein the outer elastomeric barrier layer is NBR, chloroprene rubber, or a combination thereof.

47. The elastomeric article of any one of claims 45 through 46, wherein the middle elastomeric layer is polyvinyl alcohol.

48. The elastomeric article of any one of claims 45 through 47, wherein the inner elastomeric skin-contact layer is a polyamide.

49. The elastomeric article of any one of claims 45 through 48, wherein the inner elastomeric skin-contact layer comprises nylon 6, nylon 66, nylon 69, nylon 610, nylon 612, or a combination thereof.

50. The elastomeric article of any one of claims 45 through 49, wherein the inner elastomeric skin-contact layer comprises:about 30 to about 75% by weight nylon 6;about 5 to about 80% by weight nylon 66;about 20 to about 55% by weight nylon 69;about 10 to about 80% by weight nylon 610; orabout 10 to about 80% by weight nylon 612.

51. The elastomeric article of any one of claims 45 through 50, wherein the inner elastomeric skin-contact layer comprises:i) a terpolymer comprising nylon 6, nylon 66, and nylon 69, wherein:the nylon 6 is present at about 35 to about 55% by weight;the nylon 66 is present at about 5 to about 35% by weight; andthe nylon 69 is present at about 20 to about 55% by weight in the terpolymer;ii) a terpolymer comprising nylon 6, nylon 66, and nylon 610, wherein:the nylon 6 is present at about 35 to about 75% by weight;the nylon 66 is present at about 10 to about 80% by weight; andthe nylon 610 is present at about 10 to about 80% by weight in the terpolymer; oriii) a terpolymer comprising nylon 6, nylon 66, and nylon 612, wherein:the nylon 6 is present at about 30 to about 75% by weight;the nylon 66 is present at about 10 to about 80% by weight; andthe nylon 612 is present at about 10 to about 80% by weight in the terpolymer.

52. The elastomeric article of any one of claims 45 through 51, wherein the outer elastomeric barrier layer is from about 5 mils (0.13 mm) to about 20 mils (0.51 mm)in thickness, wherein the middle elastomeric layer is from about 0.3 mil (0.07 mm) to about 10 mils (0.25 mm) in thickness, and wherein the inner elastomeric skin-contact layer is from about 0.1 mils (0.003 mm) to about 5 mils (0.13 mm) in thickness.

53. The elastomeric article of any one of claims 45 through 52 having maximum total thickness from about 6 mil (0.15 mm) to 35 mil (0.89 mm).

54. The elastomeric article of any one of claims 45 through 53, having a maximum total thickness of less than or equal to about 24 mils (0.61 mm).

55. The elastomeric article of any one of claims 45 through 54, wherein the elastomeric article is a single use glove.

56. The elastomeric article of any one of claims 45 through 54, wherein at least a portion of the inner elastomeric skin-contact layer is disposed over a woven or non-woven support.

57. The elastomeric article of any one of claims 45 through 54 wherein the elastomeric article is an industrial use glove.

58. The elastomeric article of any one of claims 45 through 57, wherein two or more of the outer elastomeric barrier layer, the middle elastomeric layer, and the inner elastomeric skin-contact layer are cured simultaneously.

59. The elastomeric article of any one of claims 45 through 58, wherein the outer elastomeric barrier layer provides greater than about 50% of a thickness of the article.

60. The elastomeric article of any one of claims 45 through 59, effective to provide a chemical permeation time in excess of 400 minutes pursuant to EN 16523-1:2015 for benchmark solvents of dichloromethane, toluene and tetrahydrofuran.

61. The elastomeric article of any one of claims 45 through 60, wherein, for permeation time measured pursuant to EN 16523-1 : 2015 and compared to a comparative for permeation time measured pursuant to EN 16523-1 : 2015 of a comparative elastomeric article having an outer elastomeric barrier layer free of NBR and chloroprene of the same thickness as the elastomeric article, the elastomeric article is effective to provide a dichloromethane chemical permeation time, an acetone permeation time, an ethyl acetate permeation time, and a methanol permeation time which is greater than the comparative permeation time for the comparative elastomeric article, wherein at least one permeation time is about five-times or greater than the corresponding comparative permeation time.

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