Unsupported chemical resistant glove

Abstract

An unsupported chemical resistant glove is disclosed herein having an inner first polymeric layer in a shape of a glove comprising polyisoprene; a middle second polymeric layer comprising polychloroprene rubber disposed directly over, and in contact with, the inner first polymeric layer, and an outer third polymer layer comprising nitrile-butadiene rubber disposed directly over, and in contact with, the middle second polymeric layer; the unsupported chemical resistant glove having a total thickness from about 0.09 mm to 0.65 mm; wherein a thickness of the inner first polymeric layer is from about 65% to 75% of the total thickness of the glove. A method of manufacturing the glove is also disclosed.

Description

UNSUPPORTED CHEMICAL RESISTANT GLOVEBACKGROUND

[0001] This application is associated with and claims priority to United States Provisional Application No. 63 / 604,639 filed on 30 November 2023, and entitled “Unsupported Chemical Resistant Glove”, which is incorporated in its entirety by reference.Field

[0002] The present application relates generally to gloves and more particularly to gloves having high chemical resistant properties, including chemical resistance to ketones.Description of the Related Art

[0003] Many workers wear gloves that provide protection from hazardous chemicals. For example, workers, and especially workers in industrial or laboratory settings, encounter many types of chemicals, e.g., acids, bases, hydroxides, aliphatic hydrocarbons, aromatic hydrocarbons, and / or aqueous or non-aqueous polar or non-polar solvents and / or solutions combining any or all of these chemicals, which may further contain hydrocarbons or have inorganic chemicals dissolved therein. However, gloves having chemical resistance to ketones, e.g., acetone, MEK, and the like, are often bulky and stiff. Moreover, workers also want flexible, comfortable gloves for extended use, so hands do not tire easily and / or to perform delicate tasks requiring dexterity. Indeed, it is common in the art for users to wear from about 5 to 7 pairs of gloves, referred to in the art as overgloving, when requiring protection from acetone and other ketones. These users are often required to change these multiple gloves frequently to minimize potential chemical exposure.

[0004] 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, overgloving a plurality of gloves that are resistant to each of these families to form a complimentary protection is necessary. An overglove, or overgloving, may be used, for example, as an additional layer of protection, whichis disposed on another glove. However, the solution of overgloving is not ergonomically practical in that it hinders handling and may render the multiple gloves too bulky when dexterity is required.

[0005] There is a need in the art to eliminate or reduce overgloving while improving the duration during which the glove acts as an effective barrier to ketones.

[0006] With the foregoing in view, the inventors herein provide composite polymeric gloves that are soft, flexible, and chemically resistant to many classes of chemicals, including ketones, and methods for manufacturing the unsupported chemical resistant gloves.SUMMARY

[0007] In embodiments, an unsupported chemical resistant glove, comprises a first polymeric layer in a shape of a glove comprising nitrile-butadiene rubber; a second polymeric layer comprising polychloroprene rubber; and a third polymer layer comprising polyisoprene rubber.

[0008] In embodiments, an unsupported chemical resistant glove comprises an inner first polymeric layer in a shape of a glove comprising nitrile-butadiene rubber; a middle second polymeric layer comprising polychloroprene rubber disposed directly over, and in contact with, the inner first polymeric layer, and an outer third polymer layer comprising polyisoprene rubber disposed directly over, and in contact with, the middle second polymeric layer, wherein the unsupported chemical resistant glove has a chemical permeation time to acetone of greater than or equal to about 15 minutes when determined according to ISO374-1 :2016.

[0009] In embodiments, a process for forming an unsupported chemical resistant glove, comprises coating a hand shaped former with a coagulant; disposing a first layer of a polymeric material comprising nitrile-butadiene rubber on the former; disposing a second layer of a polymeric material comprising chloroprene rubber directly onto and in contact with the first layer, disposing a third layer of a polymeric material comprising polyisoprene rubber directly onto and in contact with the second layer; and curing the first layer, the second layer, and the third layer; to form the unsupported chemical resistant glove; wherein theunsupported chemical resistant glove has a chemical permeation time to acetone of greater than or equal to about 15 minutes when determined according to ISO374-1 :2016.

[0010] An unsupported chemical resistant glove, substantially as shown in and / or described in connection with at least one of the figures, as set forth more completely in the claims, is disclosed. Various advantages, aspects, and novel features of the present disclosure will be more fully understood from the following description and drawings. The foregoing summary is not intended, and should not be contemplated, to describe each embodiment or every implementation of the present invention. The Detailed Description and exemplary embodiments therein more particularly exemplify various aspects and embodiments disclosed herein.BRIEF DESCRIPTION OF THE DRAWINGS

[0011] So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of this disclosure, 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 of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.

[0012] FIG. 1 depicts the palm side of an unsupported chemical resistant glove, according to embodiments of this disclosure;

[0013] FIG. 2 depicts a cross section of the unsupported chemical resistant glove of FIG. 1 according to embodiments of this disclosure;

[0014] FIG. 3 depicts an alternative cross section of the unsupported chemical resistant glove of FIG. 1 according to embodiments of this disclosure; and

[0015] FIG. 4 depicts a flow diagram for methods of manufacturing unsupported chemical resistant gloves according to embodiments of this disclosure.

[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] Embodiments according to the invention comprise unsupported chemical resistant gloves, for example, an unsupported chemical resistant glove having an inner first polymeric layer in a shape of a glove, a middle second polymeric layer disposed directly over, and in contact with, the inner first polymeric layer, and an outer third polymer layer disposed directly over, and in contact with, the middle second polymeric layer.

[0018] In embodiments, an unsupported chemical resistant glove comprises a first polymeric layer in a shape of a glove comprising nitrile-butadiene rubber; a second polymeric layer comprising polychloroprene rubber; and a third polymer layer comprising polyisoprene rubber. In embodiments, the unsupported chemical resistant glove has a chemical permeation time to acetone of greater than about 15 minutes when determined according to ISO374-1 :2016. In such embodiments the first, second and third polymeric layers do not imply a sequence or order of disposition, but instead refer to a laminate e.g., a combination comprising the first, second and third polymeric layers of nitrile-butadiene rubber, polychloroprene rubber and polyisoprene rubber, which may be arranged in any order. The inventors have discovered that a laminate comprising a first, second and third polymeric layers of nitrile-butadiene rubber, polychloroprene rubber and polyisoprene rubber, has a chemical permeation time to acetone of greater than about 15 minutes when determined according to ISO374-1 :2016.

[0019] In embodiments, the unsupported chemical resistant glove has an inner or internal (skin-contacting) first polymeric layer comprising nitrile-butadiene rubber integrally formed with middle second polymeric layer comprising polychloroprene rubber disposed directly over, and in contact with, the inner firstpolymeric layer, and an outer third polymer layer comprising polyisoprene, disposed directly over, and in contact with, the middle second polymeric layer, forming a chemical resistant glove which is chemically resistant to many classes of chemicals, including ketones.

[0020] For purposes herein, it is to be understood that unless otherwise indicated, reference to polyisoprene or polyisoprene rubber includes synthetic polyisoprene, natural rubber, or blends thereof.

[0021] The Applicants have discovered that the polychloroprene layer provides softness and flexibility when arranged as the middle layer, as well as further providing chemical resistance for various classes of chemicals, e.g., organic and inorganic acids, alcohols, alkaline solutions, and oils. The outer third polymeric layer comprising polyisoprene provides strength and chemical resistance to ketones, and other chemicals, e.g., weaker acids, such as acetic acid, salts, solutions and blends thereof. The innermost nitrile layer provides strength and chemical resistance to hydrocarbons, such as heptanes, hexanes, toluene, and xylenes solutions, and oils and blends thereof. Also, an external layer of polyisoprene rubber can be textured using salts, providing enhanced grip and durability properties.

[0022] In addition, it has been discovered that the outer third polymeric layer comprising polyisoprene provides a desired comfort and dexterity inherent to polyisoprene rubber (e.g., natural rubber) while the inner first polymeric layer comprising nitrile-butadiene prevents the polyisoprene rubber from being in contact with user’s skin, further increasing comfort to the end user.

[0023] Additionally, the soft and flexible nature of the middle polychloroprene layer is subject to physical damage during donning and doffing as well as during manufacture due to a lack of strength. This is mitigated by the physically stronger inner first polymeric layer comprising nitrile-butadiene rubber and the outer third polymeric layer comprising polyisoprene rubber, which further serves to attenuate the middle second polymeric layer comprising polychloroprene, thereby providing for enhanced chemical protection.

[0024] In embodiments of the unsupported chemical resistant glove, the outer third polymeric layer has a thickness from about 0.01 mm to about 0.5 mm. In embodiments, the outer third polymeric layer has a thickness of greater than or equal to about 0.05 mm, or greater than or equal to about 0.1 mm, or greater than or equal to about 0.2 mm, or greater than or equal to about 0.31 mm, and less than or equal to about 0.45 mm, or less than or equal to about 0.4 mm, or less than or equal to about 0.37 mm.

[0025] In embodiments of the unsupported chemical resistant glove, the middle second polymeric layer has a thickness from about 0.01 mm to about 0.4 mm. In embodiments, the middle second polymeric layer has a thickness of greater than or equal to about 0.05 mm, or greater than or equal to about 0.06 mm, or greater than or equal to about 0.07 mm, or greater than or equal to about 0.1 mm, or greater than or equal to about 0.2 mm, and less than or equal to about 0.35 mm, or less than or equal to about 0.3 mm, or less than or equal to about 0.25 mm.

[0026] In embodiments of the unsupported chemical resistant glove, the inner polymeric layer has a thickness from about 0.01 mm to about 0.4 mm. In embodiments, the inner polymeric layer has a thickness of greater than or equal to about 0.05 mm, or greater than or equal to about 0.06 mm, or greater than or equal to about 0.07 mm, or greater than or equal to about 0.1 mm, or greater than or equal to about 0.2 mm, and less than or equal to about 0.35 mm, or less than or equal to about 0.3 mm, or less than or equal to about 0.25 mm.

[0027] In embodiments of the unsupported chemical resistant glove, the outer third polymeric layer has a thickness from about 0.01 mm to about 0.45 mm, or from about 0.31 mm to about 0.37 mm. For purposes herein, glove thickness is measured at the center of the palm region of the glove. In embodiments, the middle second polymeric layer and the inner first polymeric layer each have a thickness from about 10% to about 15% of the total thickness of the glove. For example, in an embodiment wherein the unsupported chemical resistant glove has a total thickness of about 0.47 mm and the outer third polymeric layer has a thickness of about 66% of this total thickness of the glove, the outer third polymeric layer will have a thickness of about 0.31 mm. Accordingly, the middle second polymericlayer and the inner first polymeric layer will each have a thickness from about 0.06 mm to about 0.07 mm„ wherein both the middle second polymeric layer and the inner first polymeric layer measured together will have a thickness of about 0.16 mm.

[0028] The unsupported chemical resistant glove comprises a middle second polymeric layer comprising polychloroprene rubber disposed directly over, and in contact with, the inner first polymeric layer, along with an outer third polymer layer comprising polyisoprene rubber disposed directly over, and in contact with, the middle second polymeric layer. In embodiments, the unsupported chemical resistant glove comprises a plurality of layers. The various layers may be integrally formed, e.g., intermixed or intertwined at the boundary between at least one pair of layers such that the pair of layers cannot be separated from one another. In embodiments, the layers are integrally formed, e.g., intermixed or intertwined at the boundary between each pair of layers such that each pair of layers cannot be separated from one another.

[0029] In embodiments, the unsupported chemical resistant glove has a total thickness from about 0.03 mm to 1.5 mm. In embodiments the unsupported chemical resistant glove has a total thickness of greater than or equal to about 0.1 mm, or greater than or equal to about 0.15 mm, or greater than or equal to about 0.2 mm, or greater than or equal to about 0.25 mm, and less than or equal to about 1 mm, or less than or equal to about 0.9 mm, or less than or equal to about 0.8 mm, or less than or equal to about 0.7 mm.

[0030] In embodiments, the unsupported chemical resistant glove has a total thickness from about 0.0.09 mm to 0.65 mm, or from about 0.4 mm to 0.5 mm. In embodiments, the total thickness is greater than or equal to about 0.42 mm, or greater than or equal to about 0.44 mm, or greater than or equal to about 0.46 mm, or greater than or equal to about 0.48 mm, and less than or equal to about 0.55 mm, or less than or equal to about 0.50 mm.

[0031] In embodiments a thickness of the inner first polymeric layer is from about 10% to about 20% of the thickness of the outer third polymeric layer. Taking the above example, if the outer third polymeric layer has a thickness of about 0.31mm, and the inner first polymeric layer has a thickness from about 10% to about 20% of the thickness the outer third polymeric layer, this inner first polymeric layer will have a thickness from about 0.053 mm to about 0.065 mm. Accordingly, in this example, the middle second polymeric layer and the inner first polymeric layer will each have a thickness from about 0.053 mm to about 0.065 mm.

[0032] In embodiments, each of the individual layers, i.e., the inner first polymeric layer comprising nitrile-butadiene rubber, the middle second polymeric layer comprising polychloroprene rubber, and the outer third polymer layer comprising polyisoprene rubber may further comprise at least one of a vulcanizing agent, an activator, one or more surfactants, an accelerant, a crosslinker, a pigment, or any combination thereof. In some of such embodiments, one or more of the individual layers is accelerator-free.

[0033] In some embodiments, the chemical resistant glove comprises at least three layers, wherein a first of the at least three layers comprises nitrilebutadiene rubber, a second of the one of at least three layers comprises polychloroprene rubber, and a third of the one of at least three layers comprises polyisoprene rubber, wherein at least one of the three layers is disposed inbetween the other two layers. In such embodiments, the designation of first, second and third is merely for identification and does not reflect a relative location of one layer to another layer. Accordingly, in some embodiments the first layer is the outer layer; in other embodiments the second layer is the outer layer; and in still other embodiments the third layer is the outer layer.

[0034] The Applicant has discovered a non-linear relationship between a thickness of the outer third polymeric layer comprising polyisoprene rubber, and a thickness of the middle and inner first polymer layers comprising polychloroprene and nitrile-butadiene rubber, wherein a ratio of these thicknesses based on a total thickness of the glove, e.g., 65-75% to 17-21%, provides for an unexpected improvement in chemical resistance to ketones in which the chemical resistance is more than doubled compared to other arrangements. For example, it was discovered that the chemical resistance to ketones decreased significantly by nearly 100% when the ratio of the thickness of the outer third polymeric layer tothe thickness of the combined middle and inner first polymer layers was below 64%, based on a total thickness of the glove. It was further discovered that this same thickness ratio in excess of 75% resulted in a decrease of other attributes of the glove.

[0035] In embodiments, of the unsupported chemical resistant glove, the outer third polymeric layer comprises greater than or equal to about 51 wt% polyisoprene rubber, which in embodiments is natural rubber. In some embodiments, the outer third polymeric layer comprises greater than or equal to about 54 wt% polyisoprene rubber, or greater than or equal to about 68 wt% polyisoprene rubber, or greater than or equal to about 87 wt% polyisoprene rubber, or greater than or equal to about 96 wt% polyisoprene rubber. In some embodiments, the outer third polymeric layer consists of (is), or consists essentially of polyisoprene rubber.

[0036] In embodiments, of the unsupported chemical resistant glove, the second middle polymeric layer comprises greater than or equal to about 51 wt% polychloroprene rubber. In some embodiments, the second middle polymeric layer comprises greater than or equal to about 53 wt% polychloroprene rubber, or greater than or equal to about 64 wt% polychloroprene rubber, or greater than or equal to about 79 wt% polychloroprene rubber, or greater than or equal to about 98 wt% polychloroprene rubber. In some embodiments, the second middle polymeric layer consists of (is), or consists essentially of polychloroprene rubber.

[0037] In embodiments, of the unsupported chemical resistant glove, the inner first polymeric layer comprises greater than or equal to about 51 wt% nitrilebutadiene rubber. In some embodiments, the inner first polymeric layer comprises greater than or equal to about 55 wt% nitrile-butadiene rubber, or greater than or equal to about 67 wt% nitrile-butadiene rubber, or greater than or equal to about 81 wt% nitrile-butadiene rubber, or greater than or equal to about 95 wt% nitrile- butadiene rubber. In some embodiments, the inner first polymeric layer consists of (is), or consists essentially of nitrile-butadiene rubber.

[0038] In embodiments, the inner first polymeric layer comprises nitrile- butadiene rubber, carboxylated nitrile-butadiene rubber, or a combination thereof.In embodiments, the nitrile-butadiene rubber comprises, or consists of highly carboxylated nitrile-butadiene rubber, having 30% or greater carboxylation, which in embodiments is from about 30% to 40% carboxylation.

[0039] In some embodiments, the outer third polymeric layer comprises a blend of natural rubber with other elastomeric materials. In embodiments, the outer third polymeric layer comprises a blend of natural rubber with at least one of nitrile-butadiene rubber, polyisoprene rubber, styrene-butadiene rubber (SBR), chlorosulphonated polyethylene rubber (CSM), ethylene propylene diene (EPDM) rubber, polyvinyl acetate (PVA), ethylene vinyl acetate (EVA), polyvinyl chloride (PCV), polychloroprene rubber, or combinations thereof. In some embodiments, the outer third polymeric layer comprises an accelerator. In some embodiments, the outer third polymeric layer is accelerator free.

[0040] In some embodiments, the middle second polymeric layer comprises a blend of polychloroprene rubber with other elastomeric materials. In embodiments, the middle second polymeric layer comprises a blend of polychloroprene rubber and polyisoprene rubber, or a blend of polychloroprene rubber and natural rubber, or a blend of polychloroprene rubber and nitrile- butadiene rubber. In some embodiments, the middle second polymeric layer comprises an accelerator. In some embodiments, the middle second polymeric layer is accelerator free.

[0041] In some embodiments, the inner first polymeric layer comprises a blend of nitrile-butadiene rubber with other elastomeric materials. In some embodiments, the inner first polymeric layer comprises a blend of nitrile-butadiene rubber with polychloroprene rubber. In some embodiments, the inner first polymeric layer comprises an accelerator. In some embodiments, the inner first polymeric layer is accelerator free.

[0042] In some embodiments, the outer third polymeric layer comprising natural rubber, the middle second polymeric layer comprising polychloroprene rubber, and / or the inner first polymeric layer comprising nitrile-butadiene rubber, is a blend further comprising, either individually or in combination, polyisobutylene, ethylene vinyl acetate, ethylene methyl acrylate, ethylene-propylene rubber,ethylene-propylene diene rubber, polyisoprene, polyurethane, or a combination thereof.

[0043] In embodiments, each of the layers of the layers are integrally formed and each provide functionality which produces an unexpected benefit over the prior art. The prior art does not disclose or suggest the integral layers of the unsupported chemical resistant glove, i.e., the inner first polymeric layer comprising nitrile-butadiene rubber integrally formed with the middle second polymeric layer comprising polychloroprene rubber disposed directly over, and in contact with, the inner first polymeric layer, integrally formed with the outer third polymer layer comprising polyisoprene rubber disposed directly over, and in contact with, the middle second polymeric layer, which when present in the glove and in the order indicated, result in a level of chemical resistance to acetone and other ketones which is much greater than the sum of the protections conferred by each of the materials taken individually, i.e., wherein this combination has a chemical permeation time to acetone of greater than about 15 minutes when determined according to ISO374-1 :2016.

[0044] In some embodiments, the unsupported chemical resistant glove has a chemical permeation to acetone of greater than or equal to about 15 min, or, greater than or equal to about 18 min, or, greater than or equal to about 20 min, or, greater than or equal to about 25 min, when determined according to EN ISO374-1 :2016.

[0045] In some embodiments, , the unsupported chemical resistant glove further has an abrasion resistance level of 1 or higher when determined according to ANSI 105. The ANSI 105 standard rating is determined according to the number of cycles (revolutions) needed to wear through the glove, wherein the ANSI 105 scale ranges between 0-6, with 1 withstanding at least 100 cycles.

[0046] FIG. 1 depicts the palm side of an unsupported chemical resistant glove 100, according to embodiments of this disclosure. The unsupported chemical resistant glove comprises a thumb 102, an index finger 104, a middle finger 106, a ring finger 108, a little finger 110, a palm area 112 and, optionally, a beaded ring 114. An opening 116 is capable of receiving a hand for donning anddoffing the unsupported chemical resistant glove 100. In some embodiments according to the invention, grip features can be disposed into the outer third polymeric layer comprising polyisoprene rubber, as discussed further herein.

[0047] FIG. 2 depicts a cross section 200 of the unsupported chemical resistant glove 100 of FIG. 1 according to embodiments of this disclosure. The cross section 200 depicts the inner first polymeric layer 202, comprising a polymeric layer of a nitrile-butadiene rubber. The inner first polymeric layer 202 further comprises an interior surface 204, which is a skin-contacting surface. Also shown is a middle second polymeric layer 206 comprising polychloroprene and an outer third relatively thick polymeric layer 212 comprising polyisoprene rubber, which in embodiments is natural rubber.

[0048] FIG. 3 depicts an embodiment of cross section 200A, wherein the inner first polymeric layer 202A, consists of nitrile-butadiene rubber, and the middle second polymeric layer 206A consists of polychloroprene, and the outer third relatively thick polymeric layer 212A consists of polyisoprene rubber, which in embodiments is natural rubber.

[0049] In embodiments, a process for forming an unsupported chemical resistant glove, comprises coating a hand shaped former with a coagulant, which in embodiments may have a salt concentration from about 10 wt% up to saturation; disposing a first layer of a polymeric material comprising polyisoprene rubber on the former; disposing a second layer of a polymeric material comprising chloroprene rubber directly onto and in contact with the first layer, disposing a third layer of a polymeric material comprising nitrile-butadiene rubber directly onto and in contact with the second layer; and curing the first layer, the second layer, and the third layer; to form the unsupported chemical resistant glove; wherein the unsupported chemical resistant glove has a chemical permeation time to acetone of greater than about 15 minutes when determined according to ISO374-1 :2016. In some of such embodiments the polymeric material comprising polyisoprene rubber has a total solids content from about 25 wt% to 60 wt%. In some of such embodiments the polymeric material comprising chloroprene rubber has a total solids content from about 20 wt% to 55 wt%. In some of such embodiments thepolymeric material comprising nitrile-butadiene rubber has a total solids content from about 25 wt% to 55 wt%.

[0050] FIG. 4 depicts a flow diagram of method 400 for manufacturing unsupported chemical resistant gloves according to embodiments of this disclosure. The method 400 starts at 402 and proceeds to 404, at which point a former is washed, which is optional. At 406, a coagulant is applied on the former, such as by spraying or dipping into a coagulant solution and is allowed to dry as coagulant particles on the former. At 408, the former having the coagulant applied thereto is dipped into a bath comprising a polyisoprene rubber material, forming a layer comprising polyisoprene rubber thereon.

[0051] In embodiments, the polyisoprene rubber material or composition has a total solids content (TSC) of greater than or equal to about 25 wt%, or greater than or equal to about 30 wt%, or greater than or equal to about 35 wt%, or greater than or equal to about 40 wt%, or greater than or equal to about 45 wt%, or greater than or equal to about 50 wt%, or greater than or equal to about 5 wt%, and less than or equal to about 60 wt%, for example from about 25 wt% to 60 wt%. In embodiments the TSC of the polyisoprene rubber material is higher than that of the polychloroprene and / or the nitrile-butadiene material.

[0052] At 410, the former is dipped into a bath comprising a polychloroprene material, disposing a layer comprising polychloroprene on the polyisoprene rubber composition.

[0053] At 412, the former having the polychloroprene layer disposed on the polyisoprene rubber layer is dipped into a polymeric composition comprising nitrile- butadiene rubber forming a layer on the polychloroprene layer.

[0054] The method 400 proceeds to 414, wherein the layers are optionally beaded to form a cuff. At 416, all three of the layers are then cured at, for example, 100-135 degrees Celsius for 15 minutes in an oven to form the unsupported chemical resistant glove. At 418, the unsupported chemical resistant glove may be chlorinated. At 420, the unsupported chemical resistant glove may be stripped from the former by inversion such that the first layer of a polymeric material comprising polyisoprene rubber becomes the outer third polymer layer comprisingpolyisoprene rubber disposed directly over, and in contact with, the middle second polymeric layer.

[0055] It is to be understood that if a salt-texturization process is used to texture, for example, the fingertips, it is typically performed following the curing operation at 416, although it may be accomplished before 416.

[0056] In embodiments, an apparatus used to manufacture the unsupported chemical resistant glove of FIG. 1 , according to embodiments of this disclosure comprises a controller, which controls, for example, production line equipment, such as electronic circuits for controlling robots that deliver glove formers to various tanks comprising the various rubber compositions, and an oven to cure the glove. The former may be pre-heated to approximately 50-70°C, before dipping into the coagulant tank. The former may be allowed to dry in between the various dipping functions.

[0057] Optionally, embodiments according to the invention further comprise texturization on surfaces of gloves. For example, methods and technologies described in U.S. Patent Nos. 7,771 ,644 and 8,522,363, wherein salt is impregnated into a tacky outer layer, which coagulates the polymer molecules, and the salt is later dissolved with a solvent to leave multi-faceted cavities / indentations on and within a surface of the polyisoprene rubber, the entire disclosures of which are commonly assigned and incorporated by reference in entirety. Also, embodiments according to the invention further comprise an external natural rubber layer that is texturized using a textured former. In some embodiments, the textured former comprises, for example, a ceramic former having cavities disposed within a surface of the former. The cavities comprise a mean roughness depth of approximately 25-50 micrometers and may be as deep as 75 micrometers in depth. Moreover, the former may comprise peaks, which impart cavities onto a glove made therewith. In some embodiments, only the thumb and / or fingertips and / or palm areas are textured.

[0058] Optionally, methods according to embodiments of this disclosure include wherein the curing of the polymeric layers by heating the layers at a first temperature and a second curing step at a second temperature, wherein thesecond temperature is higher than the first temperature. Furthermore, optionally, methods include wherein curing processes include heating the three layers in gradients, for example, 50-90eC for 5-10 minutes and 90-135°C for 20 to 90 minutes.Embodiments

[0059] Embodiments of the instant disclosure include:E1 . An unsupported chemical resistant glove, comprising: a first polymeric layer in a shape of a glove comprising nitrile-butadiene rubber; a second polymeric layer comprising polychloroprene rubber; and a third polymer layer comprising polyisoprene rubber.E1 .1 An unsupported chemical resistant glove according to E1 , comprising: an inner first polymeric layer in a shape of a glove comprising nitrile-butadiene rubber; a middle second polymeric layer comprising polychloroprene rubber disposed directly over, and in contact with, the inner first polymeric layer, and an outer third polymer layer comprising polyisoprene rubber disposed directly over, and in contact with, the middle second polymeric layer, wherein the unsupported chemical resistant glove has a chemical permeation time to acetone of greater than about 15 minutes when determined according to ISO374-1 :2016.E2. The unsupported chemical resistant glove according to Embodiment E1 , having a total thickness from about 0.09 mm to 0.65 mm.E3. The unsupported chemical resistant glove according to Embodiments E1 -E2, wherein a thickness of the outer third polymeric layer is from about 65% to 75% of a total thickness of the glove.E4. The unsupported chemical resistant glove according to Embodiments E1 -E3, wherein the outer third polymeric layer has a thickness from about 0.31 mm to about 0.37 mm.E5. The unsupported chemical resistant glove according to Embodiments E1 -E4, wherein the middle second polymeric layer and the inner first polymeric layer each have a thickness from about 10% to about 15% of a total thickness of the glove.E6. The unsupported chemical resistant glove according toEmbodiments E1 -E5, wherein a thickness of the inner first polymeric layer is from about 10% to about 201% of a thickness of the outer third polymeric layer.E7. The unsupported chemical resistant glove according toEmbodiments E1 -E6, wherein the inner first polymeric layer comprises a blend of polychloroprene rubber and / or polyisoprene rubber with nitrile-butadiene rubber.E8. The unsupported chemical resistant glove according to Embodiments E1 -E7, wherein the outer third polymer layer comprises natural rubber.E9. The unsupported chemical resistant glove according to Embodiments E1 -E8, wherein the outer third polymer layer consists essentially of synthetic polyisoprene rubber, natural rubber, or a blend thereof.E10. The unsupported chemical resistant glove according to Embodiments E1 -E9, wherein the outer third polymeric layer comprising polyisoprene rubber is a blend further comprising polychloroprene rubber, ethylene vinyl acetate, ethylene methyl acrylate, ethylene-propylene rubber, ethylenepropylene diene rubber, chlorosulphonated polyethylene rubber, polyvinyl acetate, polyvinyl chloride, polyurethane, or a combination thereof.E11. The unsupported chemical resistant glove according to Embodiments E1 -E10, wherein the middle second polymeric layer comprising polychloroprene rubber is a blend further comprising polyisoprene rubber, nitrilebutadiene rubber, polyisobutylene, ethylene vinyl acetate, ethylene methyl acrylate, ethylene-propylene rubber, ethylene-propylene diene rubber, polyurethane, or a combination thereof.E12. The unsupported chemical resistant glove according to Embodiments E1 -E11 , wherein the inner first polymeric layer comprising nitrilebutadiene rubber, is a blend further comprising polychloroprene rubber,polyisobutylene, ethylene vinyl acetate, ethylene methyl acrylate, ethylenepropylene rubber, ethylene-propylene diene rubber, polyurethane, chlorosulphonated polyethylene rubber, polyvinyl acetate, polyvinyl chloride, or a combination thereof.E13. The unsupported chemical resistant glove according to Embodiments E1 -E12, having an abrasion resistance of greater than or equal to 1 when determined according to ANSI-105.E14. The unsupported chemical resistant glove according to Embodiments E1 -E13, wherein the outer third polymeric layer is a blend consisting essentially of polyisoprene rubber and polychloroprene rubber.E15. The unsupported chemical resistant glove according to Embodiments E1 -E14, wherein the middle second polymeric layer is a blend consisting essentially of polychloroprene rubber and polyisoprene rubber.E16. The unsupported chemical resistant glove according to Embodiments E1 -E15, wherein the middle second polymeric layer is a blend consisting essentially of polychloroprene rubber and nitrile-butadiene rubber.E17. The unsupported chemical resistant glove according to Embodiments E1 -E16, wherein the inner first polymeric layer is a blend consisting essentially of nitrile-butadiene rubber and polychloroprene rubber.E18. A process for forming an unsupported chemical resistant glove, comprising: coating a hand shaped former with a coagulant; disposing a first layer of a polymeric material comprising polyisoprene rubber on the former; disposing a second layer of a polymeric material comprising chloroprene rubber directly onto and in contact with the first layer, disposing a third layer of a polymeric material comprising nitrile-butadiene rubber directly onto and in contact with the second layer; and curing the first layer, the second layer, and the third layer; to form the unsupported chemical resistant glove according to Embodiments E1 -E17;wherein the unsupported chemical resistant glove has a chemical permeation time to acetone of greater than or equal to about 15 minutes when determined according to ISO374-1 :2016.E19. A process for forming an unsupported chemical resistant glove, comprising: coating a hand shaped former with a coagulant; disposing a first layer of a polymeric material comprising nitrile-butadiene rubber on the former; disposing a second layer of a polymeric material comprising chloroprene rubber directly onto and in contact with the first layer, disposing a third layer of a polymeric material comprising polyisoprene rubber directly onto and in contact with the second layer; and curing the first layer, the second layer, and the third layer; to form the unsupported chemical resistant glove; wherein the unsupported chemical resistant glove has a chemical permeation time to acetone of greater than about 15 minutes when determined according to ISO374-1 :2016.E20. The process according to Embodiments E18-E19, wherein the cured chemical resistant glove is removed from the former by inversion.E21. The process according to Embodiments E18-E20, wherein the polymeric material comprising polyisoprene rubber comprises natural rubber, synthetic polyisoprene rubber or blends thereof.E22. The process according to Embodiments E18-E21 , wherein the polymeric material comprising polyisoprene rubber has a total solids content from about 25 wt% to 60 wt%.E23. The process according to Embodiments E18-E22, wherein the polymeric material comprising chloroprene rubber has a total solids content from about 20 wt% to 55 wt%.E24. The process according to Embodiments E18-E23, wherein the polymeric material comprising nitrile-butadiene rubber has a total solids content from about 25 wt% to 55 wt%.E25. The process according to Embodiments E18-E24, wherein the third layer consists essentially of polyisoprene rubber.E26. The process according to Embodiments E18-E25, wherein the, the second layer consists essentially of polychloroprene rubber.E27. The process according to Embodiments E18-E26, wherein the first layer consists essentially of nitrile-butadiene rubber.E28. The process according to Embodiments E18-E27, wherein the third layer consists essentially of a blend of polyisoprene rubber and polychloroprene rubber.E29. The process according to Embodiments E18-E28, wherein the, the second layer consists essentially of a blend of polychloroprene rubber and i) polyisoprene rubber; and / or ii) nitrile-butadiene rubber.E30. The process according to Embodiments E18-E26, wherein the first layer consists essentially of a blend of nitrile-butadiene rubber and polychloroprene rubber.

[0060] Although some embodiments have been discussed above, other implementations and applications are also within the scope of the following claims. Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and scope of the present invention as defined by the following claims.

[0061] Publications and references, including but not limited to granted patents and published 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.

[0062] All ranges recited herein include ranges therebetween and can be inclusive or exclusive of the endpoints. Optional included ranges are from integervalues therebetween (or inclusive of one original endpoint), at the order of magnitude recited or the next smaller order of magnitude. For example, if the lower range value is 0.2, optional included endpoints can be 0.3, 0.4, ... 1.1 , 1.2, and the like, as well as 1 , 2, 3 and the like; if the higher range is 8, optional included endpoints can be 7, 6, and the like, as well as 7.9, 7.8, and the like. One-sided boundaries, such as 3 or more, similarly include consistent boundaries (or ranges) starting at integer values at the recited order of magnitude or one lower. For example, 3 or more includes 4 or more, or 3.1 or more.

Claims

CLAIMSWhat is claimed is:1 . An unsupported chemical resistant glove, comprising: a first polymeric layer in a shape of a glove comprising nitrile-butadiene rubber; a second polymeric layer comprising polychloroprene rubber; and a third polymer layer comprising polyisoprene rubber.

2. The unsupported chemical resistant glove of claim 1 , having a chemical permeation time to acetone of greater than about 15 minutes when determined according to ISO374-1 :2016.

3. An unsupported chemical resistant glove, comprising: an inner first polymeric layer in a shape of a glove comprising nitrilebutadiene rubber; a middle second polymeric layer comprising polychloroprene rubber disposed directly over, and in contact with, the inner first polymeric layer; and an outer third polymer layer comprising polyisoprene rubber disposed directly over, and in contact with, the middle second polymeric layer; wherein the unsupported chemical resistant glove has a chemical permeation time to acetone of greater than about 15 minutes when determined according to ISO374-1 :2016.

4. The unsupported chemical resistant glove of claim 3, having a total thickness from about 0.09 mm to 0.65 mm.

5. The unsupported chemical resistant glove of claim 3, wherein: i) the inner first polymeric layer has a thickness from about 0.01 mm to about 0.4 mm; ii) the middle second polymeric layer has a thickness from about 0.01 mm to about 0.4 mm; iii) the outer third polymeric layer has a thickness from about 0.01 mm to about 0.5 mm; or iv) a combination thereof.

6. The unsupported chemical resistant glove of claim 3, wherein: i) a thickness of the outer third polymeric layer is from about 65% to 75% of a total thickness of the glove; ii) the middle second polymeric layer and the inner first polymeric layer each have a thickness from about 10% to about 15% of a total thickness of the glove; iii) a thickness of the inner first polymeric layer is from about 10% to about 20% of a thickness of the outer third polymeric layer; or iv) a combination thereof.

7. The unsupported chemical resistant glove of claim 3, wherein the inner first polymeric layer comprises a blend of polychloroprene rubber and / or polyisoprene rubber with nitrile-butadiene rubber.

8. The unsupported chemical resistant glove of claim 3, wherein the outer third polymer layer comprises natural rubber.

9. The unsupported chemical resistant glove of claim 3, wherein the outer third polymer layer consists essentially of synthetic polyisoprene rubber, natural rubber, or a blend thereof.

10. The unsupported chemical resistant glove of claim 3, wherein: i) the outer third polymeric layer comprising polyisoprene rubber is a blend further comprising polychloroprene rubber, ethylene vinyl acetate, ethylene methyl acrylate, ethylene-propylene rubber, ethylene-propylene diene rubber, polyurethane, chlorosulphonated polyethylene rubber, polyvinyl acetate, polyvinyl chloride, or a combination thereof; ii) the middle second polymeric layer comprising polychloroprene rubber is a blend further comprising polyisoprene rubber, nitrile-butadiene rubber, polyisobutylene, ethylene vinyl acetate, ethylene methyl acrylate, ethylene- propylene rubber, ethylene-propylene diene rubber, polyurethane, chlorosulphonated polyethylene rubber, polyvinyl acetate, polyvinyl chloride, or a combination thereof; ill) the inner first polymeric layer comprising nitrile-butadiene rubber, is a blend further comprising polychloroprene rubber, polyisobutylene, ethylene vinyl acetate, ethylene methyl acrylate, ethylene-propylene rubber, ethylene-propylene diene rubber, polyurethane, chlorosulphonated polyethylene rubber, polyvinyl acetate, polyvinyl chloride, or a combination thereof; or iv) a combination thereof.11 . The unsupported chemical resistant glove of claim 3, wherein: i) the outer third polymeric layer is a blend consisting essentially of polyisoprene rubber and polychloroprene rubber;ii) the middle second polymeric layer is a blend consisting essentially of polychloroprene rubber and polyisoprene rubber or a blend consisting essentially of polychloroprene rubber and nitrile-butadiene rubber; ill) the inner first polymeric layer is a blend consisting essentially of nitrile-butadiene rubber and polychloroprene rubber; or iv) a combination thereof.

12. The unsupported chemical resistant glove of claims 1 -11 , having an abrasion resistance of greater than or equal to 1 when determined according to ANSI-105.

13. A process for forming an unsupported chemical resistant glove, comprising: coating a hand shaped former with a coagulant; disposing a first layer of a polymeric material comprising nitrile-butadiene rubber on the former; disposing a second layer of a polymeric material comprising chloroprene rubber directly onto and in contact with the first layer, disposing a third layer of a polymeric material comprising polyisoprene rubber directly onto and in contact with the second layer; and curing the first layer, the second layer, and the third layer; to form the unsupported chemical resistant glove; wherein the unsupported chemical resistant glove has a chemical permeation time to acetone of greater than about 15 minutes when determined according to ISO374-1 :2016.

14. The process of claim 13, wherein after curing, the unsupported chemical resistant glove is removed from the former by inversion.

15. The process of claim 13, wherein the polymeric material comprising polyisoprene rubber comprises natural rubber, synthetic polyisoprene rubber or blends thereof.

16. The process of claim 13, wherein: i) the polymeric material comprising polyisoprene rubber has a total solids content from about 25 wt% to 60 wt%; ii) the polymeric material comprising chloroprene rubber has a total solids content from about 20 wt% to 55 wt%; iii) the polymeric material comprising nitrile-butadiene rubber has a total solids content from about 25 wt% to 55 wt%; or iv) a combination thereof.

17. The process of claim 13, wherein: i) the third layer consists essentially of polyisoprene rubber; ii) the second layer consists essentially of polychloroprene rubber; iii) the first layer consists essentially of nitrile-butadiene rubber; or iv) a combination thereof.

18. The process of claim 13, wherein the third layer consists essentially of a blend of polyisoprene rubber and polychloroprene rubber.

19. The process of claim 13, wherein the, the second layer consists essentially of a blend of polychloroprene rubber and i) polyisoprene rubber; ii) nitrile-butadiene rubber; oriii) a combination thereof.

20. The process of claim 13, wherein the first layer consists essentially of a blend of nitrile-butadiene rubber and polychloroprene rubber.

Images