Detectable and multi-detectable articles

Abstract

This application relates to an elastomeric article, such as a glove, a composition for making the article, and a method for making the same. The elastomeric article contains particles for the detectability of the article (or a portion thereof) by a metal detector and / or an X-ray detector. The article may contain two different types of particles, one particle type selected from magnetic particles, highly conductive particles, or a combination, and the other particle type is particles containing one or more high atomic mass elements (having an atomic mass of at least 132). The particles may be coated with a corrosion inhibitor coating or may be uncoated. The composition for making the article may contain a viscosity modifier. TIFF2022511506000043.tif19128

Description

Technical Field

[0001] Cross - reference to Related Applications This application claims priority to Australian Patent Application No. 2018904670, filed on December 7, 2018, the content of which is incorporated herein by reference.

[0002] Field This application relates to elastomeric articles that are detectable by a detection device that can be used in an industry (e.g., the food industry) to detect foreign objects. The articles can be in the form of wearable articles such as gloves and finger cots. The articles can be detectable by two or more classes of detection devices (i.e., they can be "multi - detectable"). Detection devices for detecting the article or a portion thereof can be an X - ray detector and a metal detector.

Background Art

[0003] Background In the food manufacturing industry and other manufacturing industries, it is important to prevent foreign objects from contaminating the products being handled or passing through the production line. Systems for inspecting food during manufacturing and food packaged for sale to consumers need to take into account a wide range of equipment components and tools used in food preparation. Disposable gloves and finger cots made of thin films are widely used by food handlers in food production lines and other manufacturing industries to avoid food contamination due to contact with the hands of food handlers. Therefore, it is important in the food industry to ensure that gloves, finger cots, and their separated fragments do not contaminate food and the processing stream.

[0004] In such industries, detectors are already used to detect foreign objects in food. Metal detectors are used to detect ferromagnetic metal objects such as screws, metal shavings, and other metallic objects that can accidentally fall into food.

[0005] It has previously been proposed to include fine metal particles, such as ferrous metal particles, in polymer compositions used for the manufacture of disposable polymer gloves and finger sacks. Inclusion of such particles has the potential to enable gloves, finger sacks, or a portion thereof, i.e., contaminants, to be detected by a metal detector. However, there are several problems associated with this.

[0006] Firstly, there may be problems with the detectability of low levels of metal particles in contaminants. That is, due to the combination of the detector's sensitivity and a small amount of metal particles, especially when the glove or finger sack is only present in a small portion in the food, the contaminant may escape detection. Increasing the size and / or percentage amount of the particles in the composition used to make the glove / finger sack may make processing difficult during the manufacture of the glove / finger sack. Increasing the sensitivity of the detector is an alternative to increasing the particle size or loading amount, but this may not be possible due to interference caused by the nature of the food and / or the ambient electromagnetic field within the detector.

[0007] A second problem is that foods cooked in a wet state, or foods that may contain a lot of sodium or are packaged / wrapped in a metal foil package, can interfere with the ability of a metal detector to detect metal particle-containing contaminants. For example, if the food packaging is a metal foil laminate, the metal detector may not be able to distinguish between the metal-containing contaminant (glove, finger sack, or a portion thereof) and the packaging.

[0008] In the art, several glove products that are detectable by metal detectors have been reported. However, such products tend to be thick in order to sufficiently carry detectable particles or to provide the necessary tensile strength of the gloves (note that thicker films tend to be stronger and offset the weakening of the film caused by the loading of metal particles). This is particularly a problem with metal-detectable food handling gloves of the PVC type, and the weight of such metal-detectable PVC gloves is generally about 7 g, while the weight of non-detectable gloves is about 4 g. Such heavier / thicker PVC type glove products tend to reduce the "tactile sensitivity" of the product wearer (the gloves are too thick to feel through). Since the margins in the food industry are low, high-cost products for food handling are generally not acceptable. Furthermore, gloves with low sensitivity are often not commercially successful.

[0009] Another problem that can occur relates to the distribution of metal-detectable particles in the article and in the composition from which the article is manufactured. Heavy particulate matter contained in the composition for manufacturing dipped articles tends to settle in the composition and / or agglomerate into lumps. This can result in an inadequate distribution of particulate matter in the final product. This problem can be significant for certain types of elastomeric materials, particularly non-PVC type latex materials.

[0010] In food processing facilities, different types of detectors may be used at different locations to detect foreign objects. For example, metal detectors may be placed in the raw material section, while X-ray detectors may be installed in the finished product section. As a result, different glove types, one suitable for metal detection and the other suitable for X-ray detection, may need to be worn by employees working in different sections of the production line, or employees working across the entire food production line may need to constantly change glove types depending on the location as they move within the facility. To avoid this problem, it is considered advantageous in some aspects if there is a glove / finger sack product that meets the requirements of both types of detection systems.

[0011] An object of the present invention is to provide a new elastomeric article having improved detectability or improved overall properties or distribution of detectable particles in a product, or at least to provide a useful alternative to existing commercially available products.

Summary of the Invention

[0012] Summary According to the present invention, there is provided an elastomeric article comprising an elastomeric film containing one or more film layers and at least two types of particles, wherein the at least two types of particles are dispersed throughout at least one of the film layers (a) magnetic particles and / or conductive particles having an electrical conductivity of at least 3.0×10 7 S / m at 20°C, and (b) particles containing one or more high atomic mass elements having an atomic mass of at least 132 are included.

[0013] Such articles and portions thereof having a film volume of at least 0.08 mm 3 are multi-detectable. Articles or portions of a particular minimum size are detectable by one or both of a metal and an X-ray detector. The fact that an article can be detected by each type of detection system allows the article (or a portion thereof) to be detected by one form of the detector in cases where there is an impediment to the detection of the article by the second form of the detector (e.g., when metal detection is obscured by a metal foil laminate packaging). The detectors in this regard are of a type suitable for performing foreign object detection on a processing line such as a food production line.

[0014] The applicant has found that by incorporating two types of particles into one or more of the film layers in an elastomeric film, they can provide a sufficiently high level of detectability by each of two forms of detectors, thereby providing an elastomeric article having greater utility in a wide range of applications. Magnetic or conductive particles can be detected by a metal detector. Some forms of magnetic particles, such as ferrite particles, are theoretically also detectable by X-rays, but the ability to detect contaminants containing such ferrite particles may be masked or blocked by food packaging materials (e.g., metal foils). However, by incorporating particles containing one or more high atomic mass elements (e.g., barium or tungsten), the applicant has found that due to the high detectability and incorporation pattern of the high atomic mass element particles using X-ray detection, contaminants containing a combination of particles can be detected even when packaged in a metal foil.

[0015] After identifying that it is desirable for the applicant to combine two different types of particles in an elastomeric article, the applicant did not know whether it was possible to incorporate such particles into an elastomeric film in a way that does not significantly affect the film properties, particularly considering the loading levels that may be required to provide effective detectability. Furthermore, in the case of high-density particles such as magnetic particles, conductive particles, and / or particles of high atomic mass elements, there was also a potential problem of ineffective distribution across the elastomeric film-forming composition, such that even if the particles could be included in a liquid latex composition, they might not be picked up within the elastomeric film layer during article manufacture, such as by dip molding. Additionally, any modifications that need to be made to the formulation or manufacturing method need to be feasible from various perspectives, including the final film properties, color, fluidity of the mixture, strength of the film, softness of the film, flexibility of the film (as indicated by elongation), etc. In particular, for glove products, it was not easily predictable or expected to achieve the desired objective of multi-detectability while maintaining acceptable film properties.

[0016] Through the use of one or more of the techniques and components described herein, Applicant has been able to produce a product that is detectable through at least one form of detector (metal and / or X-ray), regardless of whether the product being scanned for potential contaminants (e.g., packaged food) contains metal.

[0017] According to the present invention, dispersed throughout an elastomeric film-forming composition (a) magnetic particles and / or conductive particles having an electrical conductivity of at least 3.0×10 7 S / m at 20°C, and (b) particles containing one or more high atomic mass elements having an atomic mass of at least 132 is further provided an elastomeric film-forming composition comprising.

[0018] In a preferred embodiment, the elastomeric film-forming composition further comprises a viscosity modifier. Test studies completed by Applicant demonstrate the effectiveness of the viscosity modifier in ensuring that the particles incorporated into the composition remain well-dispersed throughout the composition and are not heterogeneously trapped within or sedimented from the film layer prior to curing (especially during dip formation), but are picked up into the elastomeric film layer.

[0019] The particles in the elastomeric article may be either coated or uncoated particles. Further details regarding optional coatings of the particles in the multi-detectable article are provided below.

[0020] According to the present invention, there is further provided a method for manufacturing an elastomeric article, the method comprising: - (a) magnetic particles and / or at least 3.0×10 7The step of incorporating conductive particles having an electrical conductivity of S / m and particles containing one or more high atomic mass elements (b) (having at least 132 atomic mass) into one or more elastomeric film-forming compositions, and - A step of immersing a molding tool into the one or more elastomeric film-forming compositions or into each of the one or more elastomeric film-forming compositions to produce an article comprising one or more film layers, wherein (a) magnetic particles and / or conductive particles, and (b) particles containing one or more high atomic mass elements are dispersed throughout at least one of the film layers are included.

[0021] In the above summary of the manufacturing method, when two or more elastomeric film-forming compositions are contemplated, the different types of particles used can be incorporated into separate compositions (such that they are dispersed throughout the composition as a single particle type in the composition), or it is understood that the particles can be distributed in a combination of two (or three) particle types for any film layer composition. There are several alternative combinations that can be used to make films in which the particles are distributed throughout a particular film layer. As an example, if there are two types of particles used (e.g., magnetic particles and high atomic mass element particles, or conductive particles and high atomic mass particles) and a two-layer film is produced, each of those particle types may be present in a separate layer of the two-layer film, or the particles may be combined into one film layer (the other layer may also contain the same particle combination, or only one particle type, or no particles). In an alternative, each type (two or three types) of particle may be incorporated into the same elastomeric film-forming composition to form a film layer that contains a mixture or combination of those particles throughout. There may be additional layers that contain one, two, or three particle types, or none of the particles described in the three categories. When all three particle types are incorporated into the film, the particles may be separately included in each of the three separate layers of a three-layer film, or a combination of the particles may be included in one or both layers of a two-layer film or a single-layer film, etc.

[0022] To aid further discussion, the particles of grouping (a) can be divided into two sub-groupings, the particles (a(i)) - magnetic particles, and (a(ii)) - conductive particles. As described above, one or both of these particle types can be used with the particles (b).

[0023] When the method involves the incorporation of two particle types (i.e., (a(i)) and (b) or (a(ii)) and (b)) or all three particle types (a(i)), (a(ii)), and (b) into the same layer or multiple layers, the method comprises: - dipping a mold into the above-described elastomeric film-forming composition (containing particles (a(i)) and / or (a(ii)) and (b)); and - curing the elastomeric film-forming composition on the mold to produce an elastomeric article may be included.

[0024] The dipping step may be performed one or more times to produce multiple layers of a film containing particles (a(i)) and / or (a(ii)) and (b). One or more additional dipping steps into a film-forming composition that does not contain particles (a(i)), (a(ii)), and (b) can also be performed.

[0025] This dipping manufacturing technique is particularly suitable for the production of wearable elastomeric articles such as elastomeric gloves and finger cots, elastomeric footwear (e.g., boots, socks, etc.). Such articles are preferably the dipped articles. The method involves dipping a mold having the shape of the intended object (e.g., a hand mold, a finger mold, or a foot mold) into the elastomeric film-forming composition, with any pre- and post-steps commonly used in the dip molding of products. However, it should be noted that other elastomeric articles may be manufactured using other techniques such as extrusion molding.

[0026] In aspects of the present invention, the wearable articles described above, e.g., the glove form of the article (as well as the footwear form of the article), can additionally or alternatively function as radiation shielding articles as a result of their radiation attenuation properties. Accordingly, the present application provides for the use of the above-described elastomeric articles as radiation shielding wearable articles. The present application also provides for the use of elastomeric articles as articles that are metal detectable, X-ray detectable, and radiation attenuating. The present application further provides for the use of the above-described compositions for the manufacture of multi-detectable articles that are detectable by metal detectors and X-ray detectors.

[0027] In the process of developing the above articles, compositions, and methods, the applicant has identified additional challenges related to the manufacture of detectable articles that may apply to articles containing certain types of particles. The applicant has developed various solutions to address these problems, which more generally may apply to elastomeric articles containing one class of particles (e.g., particles (a(i)) that provide metal detectability to the article), optionally together with additional classes of particles.

[0028] One problem that arises is that some types of detectable particles can be reactive and prone to corrosion, particularly in the presence of moisture and / or oxygen. This is particularly true when corrosive metal particles are used as particles of type (a(i)), (a(ii)), or (b), and in particular applies to some classes of particles of type (a(i)) - magnetic particles or (a(ii)) - highly conductive particles. One of ordinary skill in the art would appreciate that the formation of elastomeric articles generally involves aqueous systems (e.g., aqueous elastomeric film-forming compositions for dip molding of articles), which are thought to have an adverse effect on the stability of corrosive metal particles during manufacture or in the final product.

[0029] The applicant has found that the corrosion of such particles can be reduced or avoided by introducing a protective layer surrounding the particles (particle surface) that reduces, delays, or avoids the corrosion of the particles. In particular, the particles can include a corrosion inhibitor coating. In an alternative solution, the film can be modified to include a non-coated inclusion of a corrosion inhibitor. The method of inclusion of the corrosion inhibitor into the film needs to be for creating an environment within the film that suppresses the corrosion of the corrosive particles. Materials having high magnetic properties (to provide high metal detectability), which are most desirably incorporated into an elastomeric article for enhancing magnetic detectability, tend to be materials that are prone to corrosion, and thus the above proposal addresses this potential problem. Incorporating such a coating of the particles, or a non-coated inclusion of a corrosion inhibitor into the film containing the particles, allows an elastomeric article (e.g., a glove) to be manufactured completely in various colors. This is possible because corrosion (which can lead to discoloration of the article, which can be more pronounced in lighter-colored products) is minimized or avoided. Additionally, other improvements can occur by using a coating on the particles, such as an improvement in the dispersion of the particles throughout the film-forming composition and an improvement in the uniform distribution of the particles throughout the article.

[0030] Subsequently, the present application provides an elastomeric article comprising an elastomeric film containing one or more film layers, wherein at least one film layer is coated with a corrosion inhibitor and contains magnetic particles dispersed throughout the film layer.

[0031] The corrosion inhibitor forms a protective particle coating that prevents or reduces contact between water and / or oxygen contacting the particles within the film layer during manufacture or use and the magnetic particle core.

[0032] The present application also provides an elastomeric article comprising an elastomeric film containing one or more film layers, wherein at least one film layer contains magnetic particles and a corrosion inhibitor dispersed throughout the film layer, wherein the corrosion inhibitor suppresses the corrosion of the magnetic particles in the film.

[0033] By combining these options, the present application further provides an elastomeric article comprising an elastomeric film containing one or more film layers, wherein at least one film layer comprises magnetic particles dispersed throughout the film layer, wherein the magnetic particles are coated with a corrosion inhibitor and / or the corrosion inhibitor is dispersed throughout the film layer containing the magnetic particles.

[0034] An elastomeric article containing magnetic particles and a corrosion inhibitor (as a coating or non - coating inclusion) dispersed throughout at least one of the film layers - Conductive particles having an electrical conductivity of at least 3.0×10 7 S / m at - 20 °C, and / or - Particles containing one or more high atomic mass elements having an atomic mass of at least 132 may further be included.

[0035] The conductive particles and / or high atomic mass element particles may be uncoated particles or coated particles. The coating may be a corrosion inhibitor coating.

[0036] Another problem identified by the Applicant in manufacturing the new product related to the ability to distribute detectable particles (whether they are of a single type of particle or a mixture of particle types) within the elastomeric film-forming composition such that they are well-distributed throughout the composition and then remain well-distributed throughout the final film product. As an example, particles with good magnetic detectability are very heavy and tend to sediment and / or agglomerate in the composition. The Applicant tried various approaches to effectively distribute the particles within the film-forming composition for manufacturing the dipped articles, and many of the approaches tried ended in failure. The problem was that while using various thickeners in amounts that provided suspension characteristics, it was not possible to avoid either the gelling or processing problems on the manufacturing line. Non-pseudoplastic thickeners also tended to create very thick layers of the elastomeric film-forming composition on the mold (e.g., glove-shaped mold), which had an adverse effect on the weight, thickness, sensitivity, and other properties of the final product.

[0037] The Applicant's solution to this problem was to select a specific class of viscosity modifiers, which are pseudoplastic viscosity modifiers, to address this problem. These viscosity modifiers could be used to effectively suspend the particles while avoiding processing problems in the dip molding of the article. The viscosity modifiers also made it possible to keep the particles suspended for a sufficient period to conduct effective commercial activities. The Applicant had to complete a fair amount of research to determine the appropriate amount of viscosity modifier to achieve the balance of required properties from both the perspectives of manufacturing practicality and glove properties (such as thickness, particle distribution, tensile strength, modulus, etc.).

[0038] According to this aspect, the present application provides an elastomeric article comprising an elastomeric film containing one or more film layers, wherein at least one film layer comprises - (a(i)) magnetic particles dispersed throughout the film layer, (a(ii)) at least 3.0×10 at 20 °C 7At least one type of particle selected from (a(i)) magnetic particles, and / or (b) particles containing one or more high atomic mass elements, and - A pseudoplastic viscosity modifier to achieve dispersion of the particles throughout the film layer is included.

[0039] The particles contained in the elastomeric article in this aspect of the present application can be only magnetic particles (a(i)). The particles can be magnetic particles combined with either or both of particles (a(ii)) and (b). The particles can be coated or uncoated particles as described above. Preferred features of the pseudoplastic viscosity modifier and preferred amounts of its components are as described in more detail below.

[0040] This application also - At least one type of particle selected from (a(i)) magnetic particles, (a(ii)) conductive particles having an electrical conductivity of at least 3.0×10 7 S / m at 20°C, and / or (b) particles containing one or more high atomic mass elements, and - A pseudoplastic viscosity modifier to disperse the particles throughout the composition is provided to form an elastomeric film-forming composition.

[0041] This application further provides a method for manufacturing the above-described elastomeric article, the method comprising - Mixing (a(i)) magnetic particles, (a(ii)) conductive particles having an electrical conductivity of at least 3.0×10 7 S / m at 20°C, and / or at least one type of particle selected from (b) particles containing one or more high atomic mass elements and a pseudoplastic viscosity modifier into the composition such that the particles are dispersed throughout the elastomeric article-forming composition; - Immersing a mold in the elastomeric film-forming composition; and - A step of curing an elastomeric film-forming composition on a mold to produce an elastomeric article comprises.

[0042] The method - While the mold is immersed in the elastomeric film-forming composition, a step of stirring the composition in an immersion tank to maintain the viscosity of the composition at a level lower than the viscosity of the unstirred elastomeric film-forming composition may further comprise.

[0043] Since the manufacturing method is continuous, stirring is continued during the immersion process to maintain a relatively low-viscosity composition in the immersion tank while immersed.

[0044] The prominent features of the article, composition, and method are described throughout the detailed description. [The present invention 1001] An elastomeric article comprising an elastomeric film containing one or more film layers and at least two types of particles, wherein the at least two types of particles are dispersed throughout at least one of the film layers (a) magnetic particles and / or conductive particles having an electrical conductivity of at least 3.0×10 7 S / m at 20 °C, and (b) particles containing one or more high atomic mass elements having an atomic mass of at least 132 The elastomeric article comprising. [The present invention 1002] 5.0 mm 3 or 1.0 mm 3 A part of the article is detectable by both a metal detector and an X-ray detector. The elastomeric article of the present invention 1001. [The present invention 1003] The elastomeric article according to any one of the above of the present invention, which is in the form of a wearable article. [The present invention 1004] The elastomeric article according to any one of the above of the present invention, having a thickness in the range of 0.01 mm to 3 mm. [The present invention 1005] The elastomeric article according to any one of the above of the present invention, having a 500% elongation modulus of at least 1.0 MPa. [The present invention 1006] The elastomeric article according to any one of the above of the present invention, having a 500% elongation modulus of 1.0 to 25 MPa. [The present invention 1007] The elastomeric article according to any one of the above of the present invention, having a 500% elongation modulus of 3.0 to 18 MPa. [The present invention 1008] The elastomeric article according to any one of the above of the present invention, having a tensile strength of at least 8 MPa or at least 12 MPa or at least 14 MPa or at least 16 MPa. [The present invention 1009] The elastomeric article according to any one of the above of the present invention, having a breaking elongation of at least 100% or at least 200% or at least 300% or at least 400% or at least 500%. [The present invention 1010] The elastomeric article according to any one of the above of the present invention, wherein the magnetic particles and / or conductive particles are ferrite particles, conductive particles, or a mixture thereof. [The present invention 1011] The elastomeric article according to any one of the above of the present invention, wherein the article contains the magnetic particles and the magnetic particles have an average particle size based on an average diameter of less than 5 μm or less than 2 μm. [The present invention 1012] Any elastomeric article of the present invention, wherein the article contains the magnetic particles and the magnetic particles have an average particle size based on the average diameter in the range of 0.5 to 1.5 μm in mass units. [Invention 1013] Any elastomeric article of the present invention, wherein the article contains the conductive particles and the conductive particles have an average particle size based on the average diameter of less than 30 μm or less than 20 μm or less than 15 μm. [Invention 1014] Any elastomeric article of the present invention, wherein the article contains the conductive particles and the conductive particles have an average particle size based on the average diameter in the range of 0.5 to 11 μm in mass units. [Invention 1015] Any elastomeric article of the present invention, wherein the particles containing one or more high atomic mass elements are selected from the group consisting of particles of barium compounds, particles of bismuth compounds, particles of tungsten metal or tungsten compounds, or a mixture of one or more of them. [Invention 1016] Any elastomeric article of the present invention, wherein the particles containing one or more high atomic mass elements have an average particle size based on the average diameter in the range of 0.1 to 20 μm or 0.8 to 20 μm or 0.8 to 15 μm in mass units. [Invention 1017] Any elastomeric article of the present invention, wherein the ratio of particle (a) to particle (b) is from 1:99 to 99:1. [Invention 1018] Any elastomeric article of the present invention, wherein the ratio of particle (a) to particle (b) is from 10:90 to 90:10. [Invention 1019] Any elastomeric article of the present invention, wherein the ratio of particle (a) to particle (b) is from 50:50 to 90:10. [Invention 1020] Any elastomeric article of the present invention, wherein the total amount of particles (a) and (b) is in the range of 2.0 wt% to 80 wt% of the article. [Invention 1021] Any elastomeric article of the present invention, wherein the total amount of particles (a) and (b) is in the range of 5 to 50 wt% of the article. [Invention 1022] Any elastomeric article of the present invention, wherein the total amount of particles (a) and (b) is in the range of 10 to 20 wt% of the article. [Invention 1023] The total amount of particles (a) and (b) is at least 2.0 phr and 100 phr or less, for example, 5 to 40 phr, 5 to 30 phr, 10 to 20 phr, or 5 to 15 phr, any of the elastomeric articles of the present invention. [Invention 1024] Particles (a) and (b) are combined and uniformly dispersed throughout at least one film layer, any of the elastomeric articles of the present invention. [Invention 1025] Particles (a) and (b) are uniformly distributed throughout each film layer of the elastomeric film in which they are each present, any of the elastomeric articles of the present invention. [Invention 1026] Particles (a) and (b) are uniformly distributed throughout all film layers of the elastomeric article, any of the elastomeric articles of the present invention. [Invention 1027] The article includes two or more film layers, and particles (a) and (b) are uniformly distributed throughout at least one film layer, and at least one film layer does not contain particles (a) and (b), any of the elastomeric articles of Inventions 1001 to 1025. [Invention 1028] Particles (a) are uniformly distributed in one film layer, and particles (b) are uniformly distributed throughout another film layer, and optionally, another layer does not contain particles (a) and (b), any of the elastomeric articles of Inventions 1001 to 1023. [Invention 1029] Any of the elastomeric articles of the present invention containing a viscosity modifier. [Invention 1030] The viscosity modifier is present in an amount sufficient to provide a composition for preparing the elastomeric article having a Brookfield viscosity of 50 to 1200 centipoise measured 24 hours later using a Brookfield viscometer at 25 °C, spindle number 3, and 30 rpm, the elastomeric article of Invention 1029. [Invention 1031] The amount of the viscosity modifier is sufficient to provide a viscosity of the composition of 200 to 500 centipoise, the elastomeric article of Invention 1030. [Invention 1032] Any of the elastomeric articles of the present invention containing a polyvalent metal-based crosslinking agent. [Invention 1033] The elastomer of any of the elastomer articles of the present invention is selected from the group consisting of carboxylated or non-carboxylated polyacrylonitrile butadiene, natural rubber, polyvinyl chloride, carboxylated or non-carboxylated polychloroprene, silicone rubber, polyurethane, synthetic polyisoprene, thermoplastic elastomer, and combinations or copolymers thereof. [Invention 1034] The elastomer of any of the elastomer articles of the present invention is selected from the group consisting of carboxylated or non-carboxylated polyacrylonitrile butadiene, natural rubber, carboxylated or non-carboxylated polychloroprene, silicone rubber, polyurethane, synthetic polyisoprene, and combinations or copolymers thereof. [Invention 1035] The elastomer of any of the elastomer articles of the present invention is carboxylated or non-carboxylated polyacrylonitrile butadiene. [Invention 1036] At least one type of particle present in the film, selected from the group consisting of the magnetic particles, conductive particles, and particles containing one or more high atomic mass elements having an atomic mass of at least 132, is coated with a corrosion inhibitor, in any of the elastomer articles of the present invention. [Invention 1037] Any of the elastomer articles of the present invention is in the form of an unsupported glove. [Invention 1038] Dispersed throughout the elastomer film-forming composition (a) magnetic particles and / or conductive particles having an electrical conductivity of at least 3.0×10 7 S / m at 20 °C, and (b) particles containing one or more high atomic mass elements having an atomic mass of at least 132 The elastomer film-forming composition comprising. [Invention 1039] The elastomer film-forming composition of Invention 1038, wherein the magnetic particles and / or conductive particles are ferrite particles, conductive particles, or a mixture thereof. [Invention 1040] The composition of Invention 1038 or 1039, wherein the composition contains the magnetic particles and the magnetic particles have an average particle size based on the average diameter within a range of less than 5 μm or less than 2 μm or 0.5 to 1.5 μm. [Invention 1041] The elastomeric film-forming composition according to any one of the present inventions 1038 to 1040, wherein the composition contains conductive particles, and the conductive particles have an average particle size based on the average diameter in mass units within a range of less than 30 μm, or less than 20 μm, or less than 15 μm, or 0.5 to 11 μm. [The present invention 1042] The elastomeric film-forming composition according to any one of the present inventions 1038 to 1041, wherein the particles containing one or more high atomic mass elements are selected from the group consisting of particles of barium compounds, particles of bismuth compounds, particles of tungsten metal or tungsten compounds, or a mixture of one or more of them. [The present invention 1043] The elastomeric film-forming composition according to any one of the present inventions 1038 to 1042, wherein the particles containing one or more high atomic mass elements have an average particle size based on the average diameter in mass units within a range of 0.1 to 20 μm, or 0.8 to 20 μm, or 0.8 to 15 μm. [The present invention 1044] The elastomeric film-forming composition according to any one of the present inventions 1038 to 1043, wherein the ratio of particles (a) to particles (b) is 1:99 to 99:1. [The present invention 1045] The elastomeric film-forming composition according to any one of the present inventions 1038 to 1044, wherein the ratio of particles (a) to particles (b) is 10:90 to 90:10. [The present invention 1046] The elastomeric film-forming composition according to any one of the present inventions 1038 to 1045, wherein the ratio of particles (a) to particles (b) is 50:50 to 90:10. [The present invention 1047] The elastomeric film-forming composition according to any one of the present inventions 1038 to 1046, wherein the total amount of particles (a) and (b) is at least 2.0 phr and 100 phr or less, for example, 5 to 40 phr, 5 to 30 phr, 10 to 20 phr, or 5 to 15 phr. [The present invention 1048] The elastomeric film-forming composition according to any one of the present inventions 1038 to 1047, wherein the total amount of particles (a) and (b) is 0.1 wt% to 10 wt% of the elastomeric film-forming composition. [The present invention 1049] The elastomeric film-forming composition according to any one of the present inventions 1038 to 1048, containing a viscosity modifier. [The present invention 1050] The elastomeric film-forming composition of the present invention 1049, wherein the viscosity modifier is present in an amount sufficient to provide the composition having a viscosity of 50 to 1200 centipoise measured 24 hours later using a Brookfield viscometer at 25 °C, spindle number 3, and 30 rpm. [The present invention 1051] The elastomeric film-forming composition of the present invention 1050, wherein the amount of the viscosity modifier is sufficient to provide the composition having a viscosity of 200 to 500 centipoise. [The present invention 1052] The elastomeric film-forming composition according to any one of the present inventions 1038 to 1051, containing a polyvalent metal-based crosslinking agent. [The present invention 1053] The elastomeric film-forming composition according to any one of the present inventions 1038 to 1052, comprising an elastomer selected from the group consisting of carboxylated or non-carboxylated polyacrylonitrile-butadiene, natural rubber, polyvinyl chloride, carboxylated or non-carboxylated polychloroprene, silicone rubber, polyurethane, synthetic polyisoprene, thermoplastic elastomer, and combinations or copolymers thereof. [The present invention 1054] The elastomeric film-forming composition according to any one of the present inventions 1038 to 1052, comprising an elastomer selected from the group consisting of carboxylated or non-carboxylated polyacrylonitrile-butadiene, natural rubber, carboxylated or non-carboxylated polychloroprene, silicone rubber, polyurethane, synthetic polyisoprene, thermoplastic elastomer, and combinations or copolymers thereof. [The present invention 1055] The elastomeric film-forming composition according to any one of the present inventions 1038 to 1054, having a total solid content of 5 to 50% or 5% to 40%. [The present invention 1056] The elastomeric film-forming composition according to any one of the present inventions 1038 to 1056, wherein at least one type of particle present in the film, selected from the group consisting of the magnetic particles, the conductive particles, and the particles containing one or more high atomic mass elements having an atomic mass of at least 132, is coated with a corrosion inhibitor. [The present invention 1057] The elastomeric film-forming composition according to any one of the present inventions 1038 to 1056, comprising the magnetic particles and further comprising an anticorrosive material in the elastomeric film-forming composition. [The present invention 1058] - (a) Magnetic particles and / or conductive particles having an electrical conductivity of at least 3.0×10 7 S / m at 20°C, and (b) particles containing one or more high atomic mass elements having an atomic mass of at least 132, are incorporated into one or more elastomeric film-forming compositions, and - A step of immersing a mold in one or more of the elastomeric film-forming compositions or in each of one or more of the elastomeric film-forming compositions to produce an article comprising one or more film layers, wherein (a) magnetic particles and / or conductive particles, and (b) particles containing one or more high atomic mass elements are dispersed throughout at least one of the film layers, said step A method for manufacturing an elastomeric article according to any one of elastomeric articles 1001 to 1037 of the present invention, comprising the above steps. [Inventive concept 1059] - A step of immersing the mold in an elastomeric film-forming composition according to any one of elastomeric film-forming compositions 1038 to 1057 of the present invention; and - A step of curing the elastomeric film-forming composition on the mold to manufacture the elastomeric article A method according to Inventive concept 1058, comprising the above steps. [Inventive concept 1060] An elastomeric article comprising an elastomeric film containing one or more film layers, wherein at least one film layer - (a(i)) magnetic particles dispersed throughout the film layer, (a(ii)) conductive particles having an electrical conductivity of at least 3.0×10 7 S / m at 20°C, and / or (b) particles containing one or more high atomic mass elements, at least one type of particle selected therefrom, and - A pseudoplastic viscosity modifier for achieving dispersion of the particles throughout the film layer The elastomeric article comprising the above components. [Inventive concept 1061] The elastomeric article according to Inventive concept 1060, comprising the magnetic particles. [Inventive concept 1062] The elastomeric article according to Inventive concept 1061, wherein the magnetic particles have an average particle size based on an average diameter of less than 5 μm or less than 2 μm. [Inventive concept 1063] The elastomeric article according to any one of Inventive concepts 1060 to 1062, wherein the particles are coated with a corrosion inhibitor. [Inventive concept 1064] 5.0 mm 3 or 1.0 mm 3 A part of the article as described above is detectable by a metal detector, and the elastomeric article according to any one of Inventive concepts 1060 to 1063. [Inventive concept 1065] An elastomeric article of any one of the present invention 1060 to 1064 having a thickness within the range of 0.01 mm to 3 mm. [The present invention 1066] An elastomeric article of any one of the present invention 1060 to 1065 having a 500% elongation modulus of 1.0 to 25 MPa. [The present invention 1067] An elastomeric article of any one of the present invention 1060 to 1066 having an elongation at break of at least 100% or at least 200% or at least 300% or at least 400% or at least 500%. [The present invention 1068] An elastomeric article of any one of the present invention 1060 to 1067, wherein the total amount of the particles is within the range of 2.0 wt% to 80 wt% of the article. [The present invention 1069] The elastomer is selected from the group consisting of carboxylated or non-carboxylated polyacrylonitrile butadiene, natural rubber, polyvinyl chloride, carboxylated or non-carboxylated polychloroprene, silicone rubber, polyurethane, synthetic polyisoprene, thermoplastic elastomer, and combinations or copolymers thereof, and any one of the present invention 1060 to 1068 elastomeric articles. [The present invention 1070] An elastomeric article of any one of the present invention 1060 to 1069, wherein the pseudoplastic viscosity modifier is a non-associative thickener. [The present invention 1071] - (a(i)) Magnetic particles, (a(ii)) Conductive particles having an electrical conductivity of at least 3.0×10 7 S / m at 20 °C, and / or (b) at least one type of particle selected from particles containing one or more high atomic mass elements, and - A pseudoplastic viscosity modifier for dispersing the particles throughout the elastomeric film-forming composition The elastomeric film-forming composition comprising. [The present invention 1072] The elastomeric film-forming composition of the present invention 1071, wherein the viscosity modifier is present in an amount sufficient to provide the composition with a viscosity of 50 to 1200 centipoise measured 24 hours later using a Brookfield viscometer at 25 °C, spindle number 3, and 30 rpm. [The present invention 1073] The elastomeric film-forming composition of the present invention 1071 or the present invention 1072, comprising the magnetic particles. [The present invention 1074] The elastomeric film-forming composition of the present invention 1073, wherein the magnetic particles have an average particle size based on an average diameter of less than 5 μm or less than 2 μm. [The present invention 1075] The elastomeric film-forming composition according to any one of the present inventions 1071 to 1074, wherein the particles are coated with a corrosion inhibitor. [The present invention 1076] The elastomeric film-forming composition according to any one of the present inventions 1071 to 1075, comprising an elastomer selected from the group consisting of carboxylated or non-carboxylated polyacrylonitrile butadiene, natural rubber, polyvinyl chloride, carboxylated or non-carboxylated polychloroprene, silicone rubber, polyurethane, synthetic polyisoprene, thermoplastic elastomer, and combinations or copolymers thereof. [The present invention 1077] The elastomeric film-forming composition according to any one of the present inventions 1071 to 1076, wherein the pseudoplastic viscosity modifier is a non-associative thickener. [The present invention 1078] - (a(i)) Magnetic particles, (a(ii)) Conductive particles having an electrical conductivity of at least 3.0×10 7 S / m at 20°C, and / or (b) at least one type of particle containing one or more high atomic mass elements, and a pseudoplastic viscosity modifier are mixed into the composition so that the particles are dispersed throughout the elastomeric article-forming composition; - A step of immersing a mold in the elastomeric film-forming composition; and - A step of curing the elastomeric film-forming composition on the mold to produce an elastomeric article according to any one of the present inventions 1060 to 1070 A method for manufacturing the elastomeric article, comprising. [The present invention 1079] - While the mold is immersed in the elastomeric film-forming composition, a step of stirring the composition in an immersion tank to maintain the viscosity of the composition at a level lower than the viscosity of the unstirred elastomeric film-forming composition The method of the present invention 1078, further comprising. [The present invention 1080] The method according to the present invention 1078 or the present invention 1079, wherein the composition contains the magnetic particles. [The present invention 1081] The method of the present invention 1080, wherein the magnetic particles have an average particle size based on the average diameter of less than 5 μm or less than 2 μm. [The present invention 1082] The method according to any one of the present inventions 1078 to 1081, wherein the particles are coated with a corrosion inhibitor. [The present invention 1083] The method according to any one of 1078 to 1082 of the present invention, wherein the elastomer is selected from the group consisting of carboxylated or non-carboxylated polyacrylonitrile butadiene, natural rubber, polyvinyl chloride, carboxylated or non-carboxylated polychloroprene, silicone rubber, polyurethane, synthetic polyisoprene, thermoplastic elastomer, and combinations or copolymers thereof. [The present invention 1084] The method according to any one of 1078 to 1083 of the present invention, wherein the pseudoplastic viscosity modifier is present in an amount sufficient to provide a composition having a viscosity of 50 to 1200 centipoise measured 24 hours later using a Brookfield viscometer at 25 °C, spindle number 3, and 30 rpm. [The present invention 1085] The method according to any one of 1078 to 1084 of the present invention, wherein the pseudoplastic viscosity modifier is a non-associative thickener. [The present invention 1086] An elastomeric article comprising an elastomeric film containing one or more film layers, wherein at least one film layer contains magnetic particles dispersed throughout the film layer, wherein the magnetic particles are coated with a corrosion inhibitor and / or the corrosion inhibitor is dispersed throughout the film layer containing the magnetic particles. [The present invention 1087] The elastomeric article according to 1086 of the present invention, wherein the magnetic particles are coated with a corrosion inhibitor. [The present invention 1088] The elastomeric article according to 1087 of the present invention, wherein the corrosion inhibitor is selected from the group consisting of silicone, wax, polymer, corrosion-resistant metal salt and corrosion-resistant metal, or combinations thereof. [The present invention 1089] The elastomeric article according to any one of 1086 to 1088 of the present invention, further comprising a functional layer between the magnetic particle core and the corrosion inhibitor coating. [The present invention 1090] The amount of magnetic particles coated with a corrosion inhibitor is about 2 wt% to 80 wt% of the article, or 2 to 50 wt%, 2 to 40 wt%, 2 to 30 wt%, 2 to 20 wt%, 5 to 50 wt%, 5 to 40 wt%, 5 to 30 wt%, 5 to 20 wt%, 10 to 50 wt%, 10 to 40 wt%, or 10 to 30 wt% of the article. The elastomeric article according to any one of 1086 to 1089 of the present invention. [The present invention 1091] The elastomeric article of any one of the present inventions 1086 to 1090, wherein the magnetic particles have an average particle size based on an average diameter of less than 5 μm or less than 2 μm. [The present invention 1092] 5.0 mm 3 or 1.0 mm 3 The elastomeric article of any one of the present inventions 1086 to 1091, wherein a portion of the article is detectable by a metal detector. [The present invention 1093] The elastomeric article of any one of the present inventions 1086 to 1092, having a thickness in the range of 0.01 mm to 3 mm. [The present invention 1094] The elastomeric article of any one of the present inventions 1086 to 1093, having a 500% elongation modulus of 1.0 to 25 MPa. [The present invention 1095] The elastomeric article of any one of the present inventions 1086 to 1094, having an elongation at break of at least 100% or at least 200% or at least 300% or at least 400% or at least 500%. [The present invention 1096] The elastomeric article of any one of the present inventions 1086 to 1095, wherein the elastomer is selected from the group consisting of carboxylated or non-carboxylated polyacrylonitrile-butadiene, natural rubber, polyvinyl chloride, carboxylated or non-carboxylated polychloroprene, silicone rubber, polyurethane, synthetic polyisoprene, thermoplastic elastomer, and combinations or copolymers thereof. [The present invention 1097] Dispersed throughout at least one of the film layers - Conductive particles having an electrical conductivity of at least 3.0×10 7 S / m at -20°C, and / or - Particles containing one or more high atomic mass elements having an atomic mass of at least 132 The elastomeric article of any one of the present inventions 1086 to 1096, further comprising. [The present invention 1098] The elastomeric article of any one of the present inventions 1086 to 1097, comprising a viscosity modifier. [The present invention 1099] An elastomeric film-forming composition comprising magnetic particles, wherein the magnetic particles are coated with a corrosion inhibitor and / or the corrosion inhibitor is dispersed throughout the film-forming composition. The elastomeric film-forming composition. [The present invention 1100] The elastomeric film-forming composition of the present invention 1099, wherein the magnetic particles are coated with a corrosion inhibitor. [The present invention 1101] The elastomeric film-forming composition of the present invention 1100, wherein the corrosion inhibitor is selected from the group consisting of silicone, wax, polymer, corrosion-resistant metal salt and corrosion-resistant metal, or a combination thereof. [The present invention 1102] The elastomeric film-forming composition of the present invention 1100 or 1101, further comprising a functional layer between the magnetic particle core and the corrosion inhibitor coating. [The present invention 1103] The elastomeric film-forming composition according to any one of the present inventions 1100 to 1102, wherein the amount of the magnetic particles coated with the corrosion inhibitor is about 2% to 80% by weight of the article. [The present invention 1104] The elastomeric film-forming composition according to any one of the present inventions 1100 to 1103, wherein the magnetic particles have an average particle size based on the average diameter of less than 5 μm or less than 2 μm. [The present invention 1105] The elastomeric film-forming composition according to any one of the present inventions 1099 to 1104, further comprising a viscosity modifier. [The present invention 1106] The elastomeric film-forming composition of the present invention 1105, wherein the viscosity modifier is present in an amount sufficient to provide a composition having a viscosity of 50 to 1200 centipoise measured 24 hours later using a Brookfield viscometer at 25 ° C, spindle number 3, and 30 rpm. [The present invention 1107] The elastomeric film-forming composition according to any one of the present inventions 1099 to 1106, comprising an elastomer selected from the group consisting of carboxylated or non-carboxylated polyacrylonitrile butadiene, natural rubber, polyvinyl chloride, carboxylated or non-carboxylated polychloroprene, silicone rubber, polyurethane, synthetic polyisoprene, thermoplastic elastomer, and combinations or copolymers thereof. [The present invention 1108] - A step of immersing a molding tool in the elastomeric film-forming composition according to any one of the present inventions 1099 to 1107; and - A step of curing the elastomeric film-forming composition on the molding tool to produce an elastomeric article according to any one of the present inventions 1086 to 1098 A method for producing the elastomeric article, comprising: [The present invention 1109] An elastomeric article comprising an elastomeric film containing one or more film layers, wherein at least one film layer comprises magnetic particles coated with a corrosion inhibitor and dispersed throughout the film layer. [The present invention 1110] An elastomeric article comprising an elastomeric film containing one or more film layers, wherein at least one film layer comprises magnetic particles and a corrosion inhibitor dispersed throughout the film layer, wherein the corrosion inhibitor inhibits corrosion of the magnetic particles in the film, the elastomeric article. [Inventive concept 1111] An elastomeric article produced by any of the methods of Inventive concepts 1058, 1059, 1078 - 1085, or 1108. [Inventive concept 1112] Use of any of the compositions of Inventive concepts 1038 - 1057, 1071 - 1077, or 1099 - 1107 for the manufacture of a multi - detectable wearable article detectable by a metal detector and an X - ray detector. [Inventive concept 1113] Use of any of the elastomeric articles of Inventive concepts 1001 - 1037, 1060 - 1070, or 1086 - 1098 as an article that is metal - detectable, X - ray - detectable, and radiation - attenuating.

Brief Description of the Drawings

[0045] The present invention will now be described in more detail with reference to the drawings that illustrate non-limiting examples of aspects of the present invention. [Figure 1] Figures 1(A), 1(B), 1(C), 1(D), 1(E), 1(F), 1(G), and 1(H) contain schematic views of eight alternative embodiments of the present invention containing magnetic and / or conductive particles (shown as black dots) and particles containing one or more high atomic mass elements (shown as hollow dots) present in different arrangements in a laminated elastomeric film. The film layers are marked A for the layers containing particles and B for the layers not containing particles. [Figure 2] X-ray images of gloves manufactured according to an embodiment of the present invention and square film samples obtained from comparative examples. The samples shown from left to right are of types I, III, IV, V, and II (II is a comparative example). [Figure 3]Four of the same square film samples tested in Figure 2 (I, III, IV, and V from left to right), followed by a photographed X-ray image of a 0.12 mm thick aluminum foil square (far right). [Figure 4] Shows the same X-ray image as that in Figure 3, and the corresponding bar graph below the X-ray image shows the detection intensity (Y-axis peak) for each sample (I, III, IV, and V) compared to a 0.12 mm thick aluminum film (marked with Al). [Figure 5] Schematic diagram of coated magnetic particles according to one aspect of the invention described herein. [Figure 6] Graph showing the metal detectability (y-axis) of two particulate materials (x-axis) measured by reference to an equivalent iron sphere particle size that is equally detectable as the particulate material. The particulate materials are, from left to right, coated iron particles and magnetite particles.

Mode for Carrying Out the Invention

[0046] Detailed Description Synthetic elastomer articles and methods of manufacture are described in further detail in this section.

[0047] Unless otherwise indicated, the description of the general features of the articles of the invention, the corresponding film-forming compositions, and the methods for their manufacture applies equally to - articles containing a combination of particles (a) and (b), - articles containing magnetic particles coated with a corrosion inhibitor, or magnetic particles together with a non-coated inclusion of a corrosion inhibitor, and - articles containing only one type of particle (e.g., coated or uncoated magnetic particles) together with a pseudoplastic viscosity modifier as applicable.

[0048] Elastomer Articles Examples of elastomeric articles to which the present invention is applicable include wearable articles such as gloves, finger cots, head coverings and footwear (including socks, boots, etc.). The gloves may be gloves for food contact, food processing, and biotechnology applications. The present invention also extends to other glove types including disposable gloves, surgical gloves, examination gloves, industrial gloves, laboratory gloves, irradiation gloves, industrial gloves, cleanroom gloves for the electronics industry, household gloves, etc. The article is preferably a disposable elastomeric article. The disposable elastomeric article is characterized by having a low thickness (i.e., a thin film) and being overall lightweight and low cost, so the product is suitable for disposal after being used for a certain period. The elastomeric article is preferably a disposable elastomeric article, in other words, a self-supporting film article, but the same formulation can be used for the manufacture of supported articles. An example of a supported article is a supported glove. Such gloves have a liner such as a knitted or woven liner, and the liner is immersed in an elastomeric film-forming composition to create one or more layers of an elastomeric film in which the liner is embedded. Supported articles in which an effective combination of particles (a) and (b) is incorporated throughout the elastomeric film may be suitable for various applications that do not require a high degree of sensitivity. The same applies to articles containing magnetic particles coated with a corrosion inhibitor or containing magnetic particles together with a non-coated inclusion of a corrosion inhibitor.

[0049] The article can be an immersed article (i.e., an article made from an immersed elastomeric film; note that the particles may be incorporated into the article by immersion or any other suitable technique). In some cases, immersion-molded articles are particularly preferred.

[0050] The article may include a single-layer film or two or more film layers (i.e., a multi-layer film). The number of film layers can be from 1 to 15 layers, for example, from 1 to 3 layers or from 1 to 4 layers. There may also be other coatings such as a slip coating or a powder coating to assist with wearing. Further, there may be a coagulant layer or an additional polymer coating layer (i.e., an addition to the elastomeric film layer). In some embodiments, the glove has no liner. In some embodiments, the glove is a thin film glove without a wire layer.

[0051] The thickness of the elastomer film can be, for example, in the range of 0.01 to 2.0 mm. The lower limit of the range can be 0.01, 0.02, 0.05, 0.1 or 0.2 mm. The upper limit of the thickness range can be 2.0, 1.0, 0.5, 0.4, 0.3, 0.2 or 0.1 mm. Any upper and lower limits can be combined without limitation to form a range, provided that the lower limit is less than the upper limit. Exemplary ranges are 0.01 to 0.3 mm, 0.02 to 0.2 mm, 0.05 to 0.10 mm, 0.03 to 0.08 mm, or 0.05 to 0.08 mm (for thin or disposable gloves and articles), and 0.2 to 2.0 mm for thick gloves. The thickness is preferably measured as the "average thickness" for the article. In the case of gloves, the thickness is measured using the average value of the thickness measurements obtained at three points: the cuff, the palm, and the fingers of the glove. In the case of an article other than a glove, if the article is smaller than a glove (e.g., a finger sack), a single measurement value can be obtained. In the case of other articles such as footwear or head covering, three measurement values are obtained at three spaced locations and the average value is calculated. In some glove embodiments, the glove can have a weight of about 1 to 5 grams, such as about 4 grams, or about 3 grams. Also, depending on the intended use of the glove, the weight of the glove containing particles (a) and (b) can be increased or decreased. In the case of a supported film, the weight of the article can be significantly higher. The same comments regarding film thickness and weight apply to articles containing magnetic particles coated with a corrosion inhibitor or containing magnetic particles together with a non-coated inclusion of a corrosion inhibitor. The same comments regarding film thickness and weight also apply to articles containing only one of the particle types (e.g., magnetic particles, which may or may not be coated) together with a pseudoplastic viscosity modifier.

[0052] When calculating the overall thickness of an elastomer glove, the industry standard practice (established by related standard D6319) is to measure the glove thickness at three points: the cuff, the palm, and the fingers. The finger thickness is measured 13 mm + / - 3 mm from the fingertip, the palm thickness is measured at the center of the palm, and the cuff thickness is measured 25 mm + / - 5 mm from the edge of the cuff. The average of the three measurements is taken to determine the glove thickness. The thickness measurement is carried out in accordance with the procedure specified in ASTM D3767-03 (reapproved in 2014). Briefly, this procedure involves measuring each test piece three times with a micrometer and measuring the thickness based on the median value. The micrometer can be analog or digital. As an example, a Mitutoyo analog micrometer, model 7301, or a Mitutoyo digital micrometer, model PK-101, can be used.

[0053] Despite the fact that the article contains a significant loading of particles (a) and (b) (where either or both of particles (a(i)) and (a(ii)) are present), an elastomeric article having a good modulus value at 500% elongation could be produced. The elastomeric articles of aspects of the present application have a modulus at 500% elongation of less than 25 MPa, and in the case of some elastomer types (e.g., nitrile), usually less than 18 MPa. The modulus at 500% elongation in some products according to some aspects of the present invention can be less than 25, 20, 18, 17, 16, 15, 14, 13, or 12 MPa. The modulus at 500% elongation can be greater than 1 MPa, and in some cases can be greater than 2, 3, 4, 5, 6, 6.5, 7, 7.5, or 8 MPa. The modulus at 500% elongation can be within a range based on one of the upper limits (e.g., 25, 20, 18, 15, 14, 13, or 12) with a lower limit (1, 2, 3, 4, 5, 6, 6.5, 7, 7.5, or 8), examples of which include 1 - 25, 3 - 18, 3 - 20, 3 - 25, 3 - 16, 3 - 15, 3 - 12, 5 - 12, and 7 - 12 MPa. The higher modulus ranges can be related to thicker elastomeric films. The modulus at 300% elongation can be at least 1.0 MPa, e.g., at least 1.5, 2.0, 2.5, 3.0, or 3.5 Mpa. The modulus at 300% elongation can be less than 7.0 MPa, e.g., 6.5 MPa or less or 6.0 MPa or less. The modulus value can be based on the non - degraded version, but preferably is based on the degraded version, or both the non - degraded version and the degraded version. For an article such as a glove that contains a combination of high - loading types (a) and (b) of particles (where either or both of particles (a(i)) and (a(ii)) are present), having this modulus value provides a suitable degree of softness for glove products for use in food handling and similar applications. It is particularly surprising that these values were achieved for articles containing 5 wt% (or more, e.g., 10 wt% or more) of particles (a) and (b).The same applies to articles containing magnetic particles coated with a corrosion inhibitor or containing magnetic particles together with a non-coated inclusion of a corrosion inhibitor. The above values for 300% and 500% modulus can be achieved for articles containing coated magnetic particles and / or an inclusion of a corrosion inhibitor in a film layer containing magnetic particles. The same comments also apply to articles containing only one of the particle types (e.g., magnetic particles, which may or may not be coated), together with a pseudoplastic viscosity modifier. The above values for 300% and 500% modulus are achievable for those single particle type-containing articles.

[0054] Elastomeric articles of aspects of the present application, such as gloves, have an elongation at break of at least 100%. The elongation at break may be even higher, for example, at least 200%, at least 300%, at least 400%, at least 500%, at least 550%, at least 600%, or at least 650%. For elastomeric articles containing two types of particles, it has been found that if the elongation at break exceeds 700%, the tensile strength may not be high enough. Thus, in some cases, a higher elongation at break is not recommended. The same applies to articles containing magnetic particles coated with a corrosion inhibitor or containing magnetic particles together with a non-coated inclusion of a corrosion inhibitor. The same comments also apply to articles containing only one of the particle types (e.g., magnetic particles, which may or may not be coated), together with a pseudoplastic viscosity modifier.

[0055] Despite including particles (a) and / or (b) in the article (with or without a corrosion inhibitor), the tensile strength of the article can be quite high, even for films with low thickness. The tensile strength of the manufactured and tested films was over 8 MPa, over 12 MPa, over 14 MPa, and over 16 MPa. Higher values can also be achieved for some embodiments, and tensile strengths exceeding 18, 20, 22, 25, 27, and 30 MPa are achievable.

[0056] The elastomeric gloves of the present application preferably meet or exceed ASTM D6319-00a for water leakage.

[0057] Calculations of weight, thickness, modulus, tensile strength, and elongation can be based on samples of at least 10 gloves.

[0058] Particles (a(i)) Magnetic particles Magnetic particles are particles formed of a substance having a large susceptibility to an external magnetic field. Suitable magnetic particles include ferromagnetic particles such as those formed from iron, nickel, cobalt and / or gadolinium; ferrimagnetic substances such as ferrite, magnetite and maghemite; and antiferromagnetic substances such as hematite, chromium and its oxides. These materials may exist as alloys that further contain other elements such as aluminum, barium, strontium, zinc, neodymium, yttrium and manganese. In some embodiments, the magnetic particles do not contain high atomic mass elements.

[0059] Magnetic particles are typically high-density particles. The density is typically in the range of 2.0 - 23.0 g / cm 3 Preferably 5.0 - 9.0 g / cm 3 within the range.

[0060] The average particle size of the particles (a(i)) is preferably less than 5 μm, or less than 2 μm. The preferred mass median diameter (D50) is in the range of 0.5 to 1.2 μm. The particle size is important. If the particles are too small, the particles tend to aggregate, which is not desirable in this case where dispersion throughout the film layer is desired to maintain the physical properties of the film and the detectability of the article or any part thereof (exceeding the minimum detectable volume). Apart from the rapid particle sedimentation in the film-forming composition, the particle size should not be too large to avoid a decrease in film strength. The mass average diameter is preferably 1.8, 1.6, 1.4, or 1.2 μm or less. The mass average diameter is preferably at least 0.1, 0.3, or 0.5 μm, and in some cases, it can be at least 0.6 or 0.7 μm.

[0061] (a(ii)) Conductive particles Suitable conductive materials have an electrical conductivity of at least 3.0×10 7 S / m at 20 °C, such as silver, gold, copper, aluminum, and their alloys. Non-magnetic, conductive materials are somewhat detectable (especially conductive particles having a conductivity exceeding 3.0×10 7 S / m) and can constitute part or all of the metal-detectable particles (a). In some embodiments, the conductive particles do not contain high atomic mass elements.

[0062] The conductive particles are typically high-density particles. The density is typically in the range of 2.0 to 23.0 g / cm 3 and preferably in the range of 2.5 to 20.0 g / cm 3 .

[0063] The average particle size of the particles (a(ii)) is preferably less than 30 μm, or less than 20 μm, or less than 15 μm. A preferred mass median diameter (D50) is in the range of 0.5 to 12 μm. The particle size is important. If the particles are too small, they tend to aggregate, which is not desirable in this case where dispersion throughout the film layer is desired to maintain the physical properties of the film and the detectability of the article or any part thereof (exceeding the minimum detectable volume). To avoid a decrease in film strength apart from rapid particle sedimentation in the film-forming composition, the particle size should also not be too large. The mass average diameter is preferably 1.8, 1.6, 1.4, or 1.2 μm or less. The mass average diameter is preferably at least 0.1, 0.3, or 0.5 μm and, in some cases, can be at least 0.6 or 0.7 μm.

[0064] (b) Particles containing one or more high atomic mass elements High atomic mass elements are elements having an atomic mass of at least 132, including cesium (atomic mass 132.91) and elements of higher atomic mass. This includes the Group 6 elements (elements included in the 6th row of the periodic table, i.e., the 6th period). Typically, one or more high atomic mass elements of the type (b) particles are selected from non-gaseous and non-radioactive high atomic mass elements. This class excludes elements such as radon (noble gas) and polonium, and also the Group 7 elements in radioactive or gaseous form. Among the elements, those having atomic numbers from 55 to 83, from cesium to bismuth, include the most preferred examples. The element is preferably selected from one or more of cesium, barium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, osmium, iridium, gold, and bismuth. Oxides, carbides, sulfides, sulfates, ferrites, carbonates, hydroxides, halides, tellurides, titanates, tungstates, and vanadates of these elements can be used. Combinations of one or more elements, or compounds of one or more elements, can be used. Exemplary materials meeting the description are barium compounds such as barium sulfate, lithopone and / or barium ferrite, bismuth compounds such as bismuth trioxide, bismuth oxychloride and / or bismuth vanadate, and tungsten metal or tungsten compounds such as tungsten trioxide, tungsten disulfide and / or tungsten carbide.

[0065] Particle (b) is preferably a high-density particle. The density of particle (b) can be from 4.0 to 23.0 g / cm 3 and can be. The density of particle (b) is at least 7.0 g / cm 3 , at least 10.0 g / cm 3 , at least 13.0 g / cm 3 or at least 15.0 g / cm 3and can preferably be at most 22.0, 21.0 or 20.0 g / cm 3 . Any upper and lower limits can be combined to form a range. To achieve an appropriate balance of glove properties (from the viewpoints of detectability, dispersibility and suspension), the range is preferably 7.0 to 20.0 g / cm 3 , or 15.0 to 21.0 g / cm 3 .

[0066] The particle size of the particles (b) is preferably selected for incorporation into the film. The average particle size of the particles (b) is preferably less than 20 μm. The average particle size (based on the mass average diameter - D50) is preferably <20 μm, <15 μm, <10 μm, and in some embodiments can be less than 5 μm. The average particle size based on the mass average diameter can be at least 0.1, 0.3, 0.5, or at least 1.0 μm. Any upper and lower limits can be combined to form a preferred target range for the particle size of the particles (b). A preferred mass median diameter (D50) that provides a good balance of properties is in the range of 0.5 to 15 μm, for example 1 to 5 μm. The applicant has found that if the D50 is too low, particle aggregation occurs even when other means are taken to minimize particle aggregation. This has a significant impact not only on the physical properties of the product but also on the overall minimum detectability limit.

[0067] Although it is possible for some high atomic mass elements to be present in the metal particles or conductive particles that can be present in the article of the present invention, for the purposes of this application, since their main characteristics are their magnetic or conductive properties, it should be noted that they are not classified as "high atomic mass element particles". The amount of the high atomic mass alloying element can be up to 80% by weight of the magnetic or conductive particles. If the particles have magnetic properties (a(i)) or conductive properties (a(ii)), the particles are considered to constitute particles of type (a(i)) or (a(ii)), respectively.

[0068] Also, at this point, it should be noted that the "type" of the particles refers to the volume of the particles or the object, which is characterized by a specific chemical composition and having a main function in the article (i.e., the metal detectability function or the X-ray detectability function). When two or more types are mentioned, this means that the particles of the two volumes can be characterized as different from each other from the perspective of their chemical composition. In some embodiments, there are at least two types of particles, one particle type provides metal detector detectability and the other particle type provides X-ray detectability.

[0069] Coating or encapsulation of particles A protective layer of a corrosion inhibitor can be provided on the surface of the particles (a(i)), or on the particles (a(ii)) or (b), according to a specific embodiment of the present invention. The corrosion inhibitor may encapsulate the particles or may be coated around the outside. The shape of the particles (particle core) can be spherical, rod-shaped, platelet-shaped, or amorphous.

[0070] As background, the corrosion of a specific type of particles (metal-based particles) can be caused by any of (1) oxidation (i.e., general corrosion), (2) chemical exposure to a corrosive agent (e.g., chlorine or sulfur), or (3) exposure to an acidic or basic substance in the end use (e.g., food that is acidic or basic and comes into contact with a particle-containing article such as a glove). Corrosion of types (1) and (2) is particularly related to the presence of corrosive particles that make up the particles (a(i)), (a(ii)), and / or (b) in the elastomeric film-forming composition used in the manufacture of the article. Such a composition used in dip-molded gloves is based on an aqueous suspension of an elastomeric polymer ("latex") and contains substances that include water, chlorine, and / or sulfur, which can cause corrosion of the particles and resulting discoloration.

[0071] A corrosion inhibitor is defined by ISO 8044 as "a chemical substance that, when present in a corrosion system (i.e., in a latex composition or in the final film) at an appropriate concentration without significantly changing the concentration of other corrosion agents, reduces the corrosion rate." A corrosion inhibitor forms a non-reactive (inert) layer on the surface of metal particles, providing oxidation resistance or corrosion resistance (in the environment in which it is present). The agent resists chemical / electrochemical reactions on the surface of the particles and thus at least delays (or reduces) the corrosion process. Corrosion inhibition should be sufficient so that there are no visible signs of corrosion of the particles in the product until the end of the product's shelf life. Elastomeric articles have a shelf life because their elastomeric properties deteriorate over time. The shelf life can typically be about 3 to 5 years.

[0072] Types of Corrosion Inhibitors As types of corrosion inhibitors (substances) that can be used in the embodiments of the present invention, - Silicones, such as polydimethylsiloxane and silicon dioxide, - Waxes, such as paraffin wax, microcrystalline wax, carnauba wax, and mineral wax, - Polymers, such as acrylic polymers, vinyl polymers, and epoxies (the polymer is preferably other than the main elastomeric polymer that forms the elastomeric film, and the polymeric form of the corrosion inhibitor is preferably a non-elastomeric polymer), - Corrosion-resistant metal salts (known as conversion coatings in some fields), such as metal phosphates (e.g., iron phosphate, manganese phosphate, and zinc dihydrogen phosphate), metal borates, and / or metal tungstates, and - Metal-based coatings based on corrosion-resistant metals such as stainless steel, chromium, zinc, and aluminum, i.e., corrosion-resistant metal coatings may be mentioned.

[0073] One or a combination of the above corrosion inhibitors can be used within the same class or across different classes.

[0074] The sub-class of corrosion inhibitors is hydrophobic corrosion inhibitors. Such materials inhibit corrosion by forming a hydrophobic film that repels water around the particles, protecting the core particles from corrosion caused by water. Examples include hydrophobic polymers, waxes, and silicones.

[0075] Method for applying (or forming) a corrosion inhibitor coating The particles can be subjected to a process for preparing a corrosion inhibitor coating on the particles before the preparation of the elastomeric article (i.e., before the formation of the elastomeric film-forming composition), or the coating can be prepared in situ (i.e., formed in the elastomeric film-forming composition, which then forms a film layer). Before the process for forming the elastomeric film, the methods for preparing the coated particles include (i) applying a coating material directly to the particles by spraying or wet milling or a combination of both; (ii) mixing the coating material into a mixture of the particles and a solvent; or (iii) chemically reacting the particles to be coated with a reagent to convert the particle composition on the particle surface into a corrosion-preventive material (i.e., chemical conversion coating) and include.

[0076] Pretreatment of the particles with an adhesion promoter (described below) can be carried out before step (i) and / or step (ii).

[0077] In all of the above methods, other processes can be used to assist in the dispersion of the particles and prevent aggregation, such as ultrasonic treatment.

[0078] The above method (iii) involves chemically reacting the surface of the particles with a suitable reagent such as an acid that forms the desired conversion coating upon reaction with the metal. This is typically done in the process of conversion coating, where a layer of corrosion inhibitor is chemically formed or deposited on the surface of the metal particles. Examples of suitable corrosion inhibitor coating materials that can be formed by the process of conversion coating are oxides such as iron oxide, chromates, phosphates, aluminates, oxalates, zirconates, and molybdates. In such cases, the particle core typically comprises a metal or a combination of metals in the metallic state. Thus, the conversion coating technique is only suitable for some classes of particles.

[0079] Function of the corrosion prevention layer The corrosion inhibitor coating, or layer, enables the metal particles to be incorporated into an aqueous system (e.g., an aqueous elastomeric film-forming composition) without being affected by oxidation. Thereby, metal-detectable gloves containing pure metal particles or their alloys with better magnetization or higher atomic weight elements can be manufactured without concern for the corrosion of those metals / alloys, and thus, the detectability can be enhanced. This makes it possible to reduce the amount of particles (wt% or phr) while still achieving a sufficient detectability level in a small amount of elastomeric film.

[0080] The applicant conducted tests to compare the performance of iron-based particles in either a coated or uncoated form. For the uncoated form of iron, magnetite (iron oxide) was used because this material is corrosion-resistant by itself (the corrosiveness of iron would prevent its use in an uncoated form). For the coated form of the particles, iron metal was used and coated with a silane adhesion promoter and then with paraffin wax. The metal detector strength (detectability with a metal detector) was tested for each material. With the same particle weight, the detection strength was higher for the coated iron metal than for magnetite (uncoated). This is shown in Figure 6. The detectability test is based on comparing the detection strength of specific particles with that of an iron sphere of a specific diameter, and the larger the equivalent diameter of the iron sphere, the higher the detectability. Compared with 0.5 mm for uncoated iron oxide, the metal detectability of the coated iron particles was equivalent to that of an iron sphere with a diameter of 0.7 mm. This modification thus enables the use of a smaller amount of metal particles based on a more detectable substance (e.g., iron metal) in an article, with the help of a corrosion prevention coating. This makes it possible for gloves to be fully manufactured in various colors. The coating may be a coloring layer or may provide the associated hue to the article (gloves). Otherwise, an article such as a glove may have a metallic luster derived from the metal particles.

[0081] Functional layer - Adhesion promoter The particles may further include a functional layer, which may be an adhesion promoter, between the particle core (type (a(i)), (a(ii)), or (b)) and the coating. This is schematically shown in Figure 5, where X represents the core (of type (a(i)), (a(ii)), or (b)), δ represents the adhesion promoter, and Y represents the corrosion inhibitor coating.

[0082] The promoter is a material that promotes or aids the adhesion of the coating to the particle core. The adhesion promoter may be a chemical substance containing a bifunctional group. These groups enable adhesion or reaction to the particle core material and the coating material. This layer can alternatively be described as a pretreatment layer that can react with the coating, which can be an inorganic core material and an organic coating (e.g., an organic polymer), to form a chemical bond. The adhesion promoter is particularly suitable for organic coatings and acts at the interface between an inorganic core (e.g., iron or aluminum) and a coating (e.g., acrylic) to enhance the adhesion between the two. This is an optional layer.

[0083] Examples of adhesion promoters include peroxides such as dicumyl peroxide, diamines such as 4,4′-diaminodiphenylmethane, bifunctional copolymers such as polypropylene grafted acrylic acid, silane coupling agents having functional groups containing epoxy groups, amino groups, vinyl groups, mercapto groups, and methacryloxy groups (examples of silane coupling agents are 3-aminopropyltriethoxysilane and 3-(2,3-epoxypropoxy)propyltrimethoxysilane); titanate coupling agents such as neoalkoxytitanate, zirconate coupling agents such as neoalkoxyzirconate; and aluminate coupling agents such as alkylacetoacetate aluminum diisopropylate are given as non-inclusive examples.

[0084] The relative amount of the corrosion inhibitor coating with respect to the particle core can be 5 to 50 wt%. The amount of the corrosion inhibitor coating can optionally be in the range of 10 to 35 wt% or about 10 to 15 wt% based on the total particle weight. The amount is more easily determined for coating techniques involving the addition of a coating layer to the particles. In the case of conversion coatings or when forming the coating layer in-situ, it may be more difficult to determine the relative amount. Nevertheless, for such coating techniques, the coating is sufficient to surround the core and produce an effective corrosion-resistant coating around the particles.

[0085] Amount of particles The relative amount or ratio of particle (a) to particle (b) can be roughly 1:99 to 99:1. The ratio of particle (a) to particle (b) is preferably 10:90 to 90:10. In some embodiments, the ratio of particle (a) to particle (b) is 50:50 to 90:10. These ratios apply regardless of whether (a) refers to only the particles of (a(i)), only the particles of (a(ii)), or a combination of the particles of (a(i)) and (a(ii)). When both particle (a(i)) and (a(ii)) are present, the relative amount of these particles is 10:90 to 90:10. When all three particle types are incorporated together, the relative amount or ratio of particle (a(i)) to particle (a(ii)) to particle (b) can be roughly between 1:1:98, 1:98:1, and 98:1:1, or between 10:10:80, 10:80:10, and 80:10:10. In some embodiments, the ratio of particle (a) to particles (b) and (c) is 30:20:50. When the particles are particles of type (a(i)) coated, these particles may be present without the incorporation of particle (a(i)) and (b).

[0086] The total amount of particles can be roughly in the range of 2 wt% to 80 wt% of the article. In certain embodiments, the amount is at least 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% or 10 wt% of the article at a minimum. For metal detection only, gloves having 0.05 wt% of particles (a) are detectable, while X-ray detection of the gloves is enhanced when using at least (about) 2.0 wt% of particles (b). For this reason, the preferred total amount of particles (a) and (b) is at least about 2.0 wt%. To achieve the best film properties, the amount preferably does not exceed 60 wt%, 50 wt%, 40 wt% or 30 wt% of the article. Any minimum and maximum values can be combined without limitation to form a range. When the amount is about 5 wt% to 40 wt% or 5 wt% to 30 wt%, or 10 wt% to 30 wt% of the article, a good balance is achieved between film properties (i.e., the amount is not so high as to degrade the film properties to an extent that an article such as a glove is considered commercially unacceptable in the market), but due to the balance of particle types, it is notable that the required minimum detectability of the article is achieved (small pieces can be detected). This range is particularly suitable for products having a thickness of 0.05 to 3 mm, for example 0.05 to 2 mm, preferably 0.05 to 1 mm, but products having a thickness outside this range are also included in this application.

[0087] The amounts of particles (a(i)), (a(ii)), and / or (b) can alternatively be calculated with reference to the part of rubber / elastomer in the product (per 100 parts of rubber / elastomer). The total amount of particles can be 2 to 100 phr in some embodiments. For metal detection only, the amount of particle (a) can be at least 0.05 phr to manufacture a metal-detectable product, while for X-ray detection, the amount of particle (b) is preferably at least 2.0 phr for enhancing X-ray detection. Overall, the amounts of particles (a) and (b) should be at least (about) 2.0 phr for multi-detectability. The minimum amount can be at least 5 or at least 10 phr, and the maximum amount can be 50 phr or less, 40 phr or less, or 20 phr or less. Suitable ranges include 5 to 40 phr and 10 to 20 phr to provide a suitable balance among detectability, good suspension in the film-forming composition, and good maintenance of elastomer film properties.

[0088] The total amount of particles (a) and (b) affects the minimum detectability (minimum detectable volume) of a portion of the article. The applicant has conducted tests to determine to what extent the minimum detectability can be achieved using the articles of the present application. The applicant has manufactured gloves containing 80 wt% of a combination of particles (a) and (b) (these particles are present in a ratio of 90:10). The product was detectable by metal detection at a volume of 0.08 mm 3 and by X-ray detection at a volume of 0.05 mm 3 . The metal detection in this test was set with the detection sensitivity of iron (Fe) with a diameter of 0.5 mm. X-ray detection was performed by testing against 0.12 mm thick aluminum foil as the detection baseline. Therefore, this test study demonstrated that detectability at 0.1 mm 3 is achievable with the concept of the present application. For products containing a smaller volume of particles, the good target minimum detectability can be higher than this and can be very commercially useful. Therefore, in some embodiments, the product has a size of 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1.0 mm 3Detectable by both metal detection and X-ray detection (beyond a 0.12 mm thick aluminum film) with the sample volume being as described.

[0089] Figures 1(A), 1(B), 1(C), 1(D), 1(E), 1(F), 1(G), and 1(H) show some alternative arrangements for the distribution of particles for the manufacture of a multi-detectable article having particles (a) (which can be of type (a(i)) and / or (a(ii))) and (b). Particles (a) and (b) may be present in separate film layers, as shown in Figures 1(F) and 1(G), where the article includes two or more film layers. The particles are uniformly distributed throughout the film layer in which they are present. In the case of Figure 1(G), there are also film layers that do not contain each of particles (a) and (b).

[0090] Particles (a(i)), (a(ii)), and (b) may be combined and uniformly dispersed throughout at least one film layer. This may be the only film layer of a single-layer elastomeric film article (Figure 1(E)). Alternatively, particles (a) (which can be (a(i)) and / or (a(ii)) particles) and (b) may be uniformly distributed throughout each film layer or all film layers of an elastomeric article, as illustrated in Figure 1(A).

[0091] In other embodiments, particles (a) and (b) may be uniformly distributed in more than two layers of the multilayer film in combination. In this case, there may be additional layers of film that do not contain particles (a) and (b). Three such arrangements are shown in FIGS. 1(B), 1(C), and 1(D). In FIG. 1(B), the particles are in two layers, and the outer film layer of the multilayer film does not contain particles. In FIG. 1(C), neither of the outer film layers contains particles (a) and (b). In FIG. 1(D), film layers that do not contain particles and film layers that contain particles are present alternately. The advantage of the arrangements shown in FIGS. 1(B) and 1(C) is that the layer that does not contain particles can be colored. In combination with the selection and incorporation of particles (a) and (b), this arrangement enables the production of colored articles that do not have the gray appearance that might otherwise be associated with elastomeric articles containing iron-based particles. The pigments and arrangements described herein enable the production of articles such as gloves in any desired color.

[0092] For embodiments based only on coated particles of type (a(i)), or on only one type of particle (e.g., magnetic particles, coated or uncoated, with a pseudoplastic viscosity modifier), the same arrangements and amounts can be applied, provided that the removal of type (b) particles is involved. The amount of particles a(i) can be about 2 - 80 wt% of the article, preferably 2 - 50 wt%, 2 - 40 wt%, 2 - 30 wt%, 2 - 20 wt%, or 5 - 50 wt%, 5 - 40 wt%, 5 - 30 wt% or 5 - 20 wt%, or 10 - 50 wt%, 10 - 40 wt%, 10 - 30 wt% of the article. When all three types of particles are present (whether or not they are coated), the particles of types (a(i)) and (a(ii)) may be present in the same layer in combination, or they may be present in separate layers. One of those particle types can be combined with the type (b) particles. All permutations are possible.

[0093] The particles are preferably well-dispersed in the elastomeric film-forming composition. This is applied to the composition during the manufacture of the article, in particular to ensure a uniform distribution within the film layer. The particles must not be in the form of aggregates (note that aggregates include strongly bound assemblies of particles that are difficult to de-aggregate). In some embodiments of the invention, this is achieved by using a pseudoplastic viscosity modifier to disperse the particles throughout the elastomeric film-forming composition. This viscosity modifier is very effective in maintaining the dispersion of the particles for a sufficiently long time to maintain well-dispersed, non-aggregated particles in the final product manufactured from the composition. The particles can be coated and surface-treated. The particles are uniformly distributed in the film layer in which they are present.

[0094] elastomer The elastomeric film-forming composition contains an elastomer-forming polymer (or simply polymer) in suspension or emulsion form. The polymer can be a natural rubber or a synthetic polymer. The polymer can be crosslinked to produce an elastomeric film. The polymer can be a single polymer or a combination (blend) of two or more polymers. Each polymer can be a homopolymer or copolymer, a grafted or modified polymer, or a blend thereof.

[0095] The polymer can contain free ionic crosslinkable groups, covalent crosslinkable groups, or a combination of both. Examples of ionic crosslinkable groups are acids including carboxylate, sulfonate and acid anhydrides, and an example of a covalent crosslinkable group is a double bond.

[0096] The polymer can be selected from rubber (natural or synthetic), nitrile rubber, polyurethane, silicone rubber, polyisoprene, polychloroprene, acrylic polymers (including acrylic diene block copolymers), styrene-butadiene, polybutadiene, copolymers of these and other polymers / monomers (random copolymers, block copolymers, etc.) and modified forms of these polymers or copolymers (e.g., polymers containing additional substituents such as carboxylates, sulfonates, halides or other substituents), and thermoplastic elastomers. Examples of suitable thermoplastic elastomers include block copolymers such as styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene-butadiene-styrene; thermoplastic polyurethanes and thermoplastic polyamides; thermoplastic vulcanizates such as vulcanized PP / EPDM compounds; copolyester elastomers; metallocene-catalyzed polyolefin elastomers such as ultra-low molecular weight, linear low density polyethylene (VLMW-LLDPE); and reactor-made thermoplastic polyolefin elastomers. The article is generally a PVC-free article.

[0097] One class of polymers that can be used are those obtained by copolymerization of conjugated diene monomers and ethylenically unsaturated acid monomers (carboxylated polyacrylonitrile butadiene is an example of such a copolymer), synthetic polyisoprene, polychloroprene, styrene copolymers and / or polyurethanes. Among the range of conjugated diene monomers, examples are 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, chloroprene and acrylonitrile. With respect to the ethylenically unsaturated acid monomers, the acid group can be a carboxyl group, a sulfonic acid group or an acid anhydride group. Examples of ethylenically unsaturated acid monomers include acrylic acid or methacrylic acid; itaconic acid, maleic acid, fumaric acid, maleic anhydride, citraconic anhydride, styrenesulfonic acid, monobutyl fumarate, monobutyl maleate, mono-2-hydroxypropyl maleate, and their alkali metal or ammonium salts. The polymers used can be carboxylated or non-carboxylated as desired.

[0098] One notable example of a suitable polymer is polyacrylonitrile butadiene. This can be carboxylated or non-carboxylated. It can be provided as a mixture of carboxylated nitrile latex and nitrile butadiene rubber.

[0099] Carboxylation refers to the presence of carboxylate (carboxylic acid or ester) groups on the polymer chain. Carboxylation can be achieved by forming the polymer with a monomer containing a carboxylate group or by grafting a carboxylate group onto the polymer. For examples of suitable carboxylated polymers, reference is made to PCT / AU2014 / 000726 and PCT / AU2014 / 000727, each of which is incorporated herein by reference in its entirety. The degree of carboxylation can be 5 to 15%, or 5 to 10%.

[0100] When manufacturing gloves using an immersion process, the polymer is initially provided in the form of an aqueous suspension. The aqueous suspension preferably has a pH of at least 9.0. The elastomeric film-forming composition may also be referred to as a "synthetic latex composition" or a "latex composition". In the art, it is common to use the expressions "latex" or "rubber" to refer to any polymer in a general sense, and the "latex composition" is used in a corresponding manner. It is understood that latex does not refer to natural rubber latex.

[0101] In the technical field of the present invention, it is common for the amount of the elastomer-forming polymer to be 100 phr (parts per hundred parts of "rubber"), and the relative amounts of the remaining components of the composition for manufacturing the elastomeric film are calculated as the number of parts by weight compared to 100 phr of the elastomer-forming polymer. Thus, for the amount of the crosslinking agent, which is 1 / 100 of the amount of the elastomer-forming polymer in the composition, the amount of the crosslinking agent is called 1.0 phr.

[0102] Other components used to manufacture elastomeric articles The elastomer-forming polymer is crosslinked with one or more crosslinking agents to produce an elastomeric film. Various types of crosslinking agents can be used. Other agents that may be present in the composition used to manufacture the elastomeric film-forming composition include viscosity modifiers, softeners, anti-ozone agents, stabilizers such as pH stabilizers, surfactants, emulsifiers, antioxidants, vulcanizing agents, polymerization initiators, pigments, fillers, colorants, and sensitizers. Many of these agents are added in granular form. Others are added as liquids. These are added before shaping the latex composition (i.e., the elastomeric film-forming composition) into the shape of a synthetic elastomeric article. In some embodiments, they are added simultaneously with the crosslinking agent. In other embodiments, they are added later.

[0103] One important component of the elastomeric film-forming composition that addresses high loading of particulate materials without sedimentation is the viscosity modifier, which will be described in more detail below.

[0104] Crosslinking agent The crosslinking agent class includes ionic crosslinking agents and covalent crosslinking agents. One or more crosslinking agents used in the manufacture of elastomeric gloves can be selected from ionic crosslinking agents, covalent crosslinking agents, and combinations thereof.

[0105] Ionic crosslinking agents include polyvalent metal-based crosslinking agents. Examples of ionic crosslinking agents include polyvalent metal oxide crosslinking agents (e.g., zinc oxide and magnesium oxide), peroxides (e.g., 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, which can be purchased under the trade name Trigonox 29-40B-pd), and solubilized ionic crosslinking agents, such as polyvalent metal polyoxides (e.g., sodium aluminate), polyvalent metal hydroxides, and polyvalent metal salts - especially solubilized trivalent metal-based crosslinking agents. Among those known in the art, other ionic crosslinking agents are used in particular. These include the crosslinking agents described in PCT / AU2016 / 050308, PCT / AU2016 / 050311, and PCT / AU2016 / 050312, each of which is incorporated by reference in its entirety.

[0106] Covalent crosslinking agents include organic crosslinking agents, sulfur, and / or sulfur donors, and combinations thereof.

[0107] Sulfur can be added in the form of elemental sulfur. Sulfur can be added in the form of a sulfur donor. Examples of suitable sulfur donors include carbamates, such as thiocarbamates (e.g., zinc dibutyldithiocarbamate (ZDBC), zinc diethyldithiocarbamate (ZDEC); zinc dimethyldithiocarbamate (ZDMC)); thiurams (e.g., tetraethylthiuram disulfide (TETD), tetramethylthiuram disulfide (TMTD)); dipentamethylenethiuram tetrasulfide (DPTT); dipentamethylenethiuram hexasulfide (DPTH); dipentamethylenethiuram hexasulfide; thioureas (ethylthiourea (ETU) and diphenylthiourea (DPTU)); thiazoles (e.g., mercaptobenzothiazole (MBT), mercaptobenzothiazole disulfide (MBTS), zinc 2-mercaptobenzothiazole (ZMBT)); guanidines (e.g., diphenylguanidine (DPG)), and aldehyde / amine-based sulfur donors (e.g., hexamethylenetetramine). Other examples are well known in the art and can be obtained from various publicly available sources.

[0108] Other crosslinking agents that can be used include crosslinkable monomers, reactive oligomers, polyisocyanate oligomers, functional crosslinking polymers, derivatives of ethylene glycol di(meth)acrylate (e.g., ethylene glycol diacrylate, di(ethylene glycol) diacrylate, tetra(methylene / ethylene glycol) diacrylate, ethylene glycol dimethacrylate (EDMA), di(ethylene glycol) dimethacrylate (DEDMA), tri(methylene / ethylene glycol) dimethacrylate, tetraethylene glycol dimethacrylate (TEDMA)), derivatives of methylene bisacrylamide (e.g., N,N'-methylene bisacrylamide, N,N'-(1,2-dihydroxyethylene) bisacrylamide), formaldehyde-free crosslinking agents (e.g., N-(1-hydroxy-2,2-dimethoxyethyl) acrylamide), divinylbenzene, divinyl ether, diallyl phthalate, divinyl sulfone, trimethylolpropane trimethacrylate (TMPTMA), polyfunctional crosslinking agents, etc. Combinations of these crosslinking agents can also be used.

[0109] Generally, any amount of crosslinking agent can be used as needed for the final article properties. Thus, the total amount of crosslinking agent in the composition can be from 0.01 to 14 phr. However, it is usually desirable to minimize the amount of crosslinking agent (and associated costs or drawbacks). The total crosslinking agent amount can be within one of the following ranges: 0.01 - 14.5 phr, 0.2 - 12.5 phr, 0.3 - 10 phr, 0.1 - 10 phr, 0.2 - 10 phr, 0.3 - 9 phr, 0.5 - 9 phr, 0.8 - 9 phr, 0.3 - 8 phr, 0.5 - 8 phr, 0.8 - 6 phr, 1 - 5 phr, 2 - 9 phr, 3 - 10 phr, 3 - 7 phr, 1 - 3 phr, 0.01 - 0.5 phr, 0.01 - 1.0 phr.

[0110] The amount of the ionic crosslinking agent can be 0.0 - 6.0 phr, for example, 0.01 - 6.0, or 0.01 - 5.0 phr. The amount is preferably even lower, 0.01 - 3.0 phr, or 0.01 - 2.0 phr, 0.01 - 1.0 phr, 0.01 - 0.7 phr, 0.01 - 0.6 phr, or 0.01 - 0.5 phr.

[0111] The amount of sulfur can be 0.0 - 5.5 phr. The amount can be even lower, 0.0 - 3.5 phr, for example, 0.01 - 3.0 phr, 0.01 - 2.0 phr, 0.01 - 1.5 phr, 0.01 - 1.0 phr, 0.01 - 0.7 phr, 0.01 - 0.5 phr, or 0.01 - 0.3 phr.

[0112] The amount of the sulfur donor can be 0.0 - 2.0 phr, for example, 0.01 - 1.5 phr, 0.01 - 1.0 phr, 0.2 - 1.0 phr, 0.01 - 0.7 phr, 0.01 - 0.5 phr, 0.01 - 0.3 phr, 0.05 - 0.2 phr, 0.3 - 2.0 phr, 0.3 - 1.5 phr, or 0.2 - 0.6 phr.

[0113] The amount of the organic crosslinking agent can be 0.0 - 4.0 phr, for example, 0.01 - 4.0. The amount can be even lower, 0.01 - 3.0 phr, or 0.01 - 2.0 phr, or 0.01 - 1.0 phr.

[0114] The crosslinking agent can be combined with the other components of the latex composition and the elastomeric film-forming composition at a suitable time to form the desired type of film. The crosslinking agent is typically added to the latex composition together with the other components. However, for some forms of the crosslinking agent (e.g., a solubilized ionic crosslinking agent containing sodium aluminate), there is a preliminary step that includes forming a crosslinkable composition and combining this with the latex under controlled conditions, followed by the addition of the other components and a second crosslinking agent.

[0115] Crosslinkable composition In some embodiments, a crosslinkable composition comprising a trivalent metal-based crosslinking agent is used. This is preferably in the form of a formulation comprising a solution of a trivalent metal source, (ii) a strong hydroxide (e.g., sodium hydroxide, potassium hydroxide, ammonium hydroxide, or combinations thereof) having a pH of at least 9.0, and optionally (iii) a mechanical stabilizer, combined together. This crosslinkable composition is as described in any of PCT / AU2016 / 050308, PCT / AU2016 / 050311, and PCT / AU2016 / 050312, referred to above. The trivalent metal is preferably aluminum, but this can be exchanged with any of the sources described in the referenced PCT applications. The selection of this crosslinking agent in a formulation providing about 0.1 to 0.5 phr of a trivalent metal source (e.g., sodium aluminate, aluminum hydroxide, or a soluble aluminum salt) enables the formation of a film with suitable properties, even in the case of high loading amounts of particles (a) and (b). The results presented herein show a significant improvement in film properties using the selection of this crosslinking agent compared to a comparative formulation without this reagent. The amount of the strong hydroxide is preferably 0.01 to 5 phr and is typically within a ratio of 2:1 to 1:2 (based on phr) relative to the trivalent metal source. Thus, the amount can be, in some embodiments, 0.05 to 1.0 phr. The strong hydroxide in this crosslinkable composition not only affects the pH of the crosslinkable composition but also has an impact on the stability of the complex ions formed from the trivalent metal source in solution and affects the activation of the trivalent metal. The mechanical stabilizer in this composition can be a water-miscible or water-soluble organic polyol, or a water-soluble or water-miscible thickening agent, examples of which are well known in food or pharmaceutical manufacturing. The amount of this agent can also be 0.01 to 5 phr and, in some embodiments, is within a ratio of 2:1 to 1:2 (based on phr) relative to the trivalent metal source. The amount can be, for example, 0.05 to 1.0 phr, or 0.05 to 4.0 phr, 0.05 to 3.0 phr, 0.05 to 2.0 phr, 0.1 to 2.0 phr, 0.5 to 3.0 phr, 0.5 to 2.0 phr, or 0.1 to 1.0 phr.Examples of such polyols and thickeners include glycerin, saccharides and sugar alcohols, maltodextrin, polysaccharides, polyglycerol, starch, modified starch, and mixtures thereof.

[0116] First, when using such a crosslinkable composition as a crosslinking agent (or one of the crosslinking agents), a relatively high concentration of the crosslinkable composition is prepared and then diluted before use. The relative amounts of the components used in the production of the high-concentration crosslinkable composition are, per 100 parts by weight of water, - 0.01 to 5 parts of a trivalent metal source; and - 0.01 to 5 parts of a strong hydroxide (preferably 0.05 to 4 parts when using the above component (a), 0.05 to 3 parts when using the above component (b), or 0.05 to 4 parts when using the above component (c)), and optionally - 0.03 to 15 parts of a mechanical stabilizer (i.e., the total stabilizer in the case of a mixture; preferably 0.5 to 3 parts) can be.

[0117] Dilution is usually carried out to reduce the concentration so that the trivalent metal ion concentration drops to 0.33 to 3.3% by weight of the crosslinkable composition. The amount used in phr of rubber is usually 0.01 to 0.5 phr based on the trivalent metal source (0.01 to 0.5 phr for the strong hydroxide, 0.03 to 1.5 phr for the stabilizer).

[0118] Other components of the elastomeric article-forming composition A preferred component of the composition is a viscosity modifier.

[0119] The high density heavy particles (a) and (b) tend to settle within the elastomeric article forming composition. Similarly, the same is true for coated magnetic particles, which are typically also high density and heavy, or uncoated particles of type (a) or (b). As a result of considering and testing several options, it was found that a viscosity modifier can be used to suspend the particles and stabilize the dispersion of the particles. There was uncertainty as to whether the viscosity modifier was effective in effectively suspending the particles, especially considering the weight of the particles, and whether the increase in viscosity would adversely affect the ability to form a film of the required thickness suitable for manufacturing thin film articles such as gloves from the composition. There was also uncertainty about the flow characteristics of the composition, which could potentially adversely affect the mechanism operating the manufacturing line for dipped articles. Another potential problem was the potential entrapment of air in the film-forming composition, which would create air bubbles on the surface of the composition during dipping. Air bubbles are a problem because they create weak areas or pinholes in the product and are unacceptable in thin film barrier products such as gloves.

[0120] Ultimately, it was found that by using a viscosity modifier that imparted pseudoplastic characteristics (i.e., a pseudoplastic viscosity modifier), a balance could be achieved between suspending the particles while avoiding overly high viscosities and entrapment of air bubbles. Due to the pseudoplastic characteristics, the viscosity can be lowered by an increase in shear force due to agitation. By increasing the agitation (stirring) of the composition, the viscosity can be reduced by at least 25%. In some cases, the pseudoplastic viscosity modifier can cause a viscosity reduction of about 50% (e.g., within a range of 25% - 70% viscosity reduction, or 30% - 70% viscosity reduction, measured in centipoise), which helps to release the entrapped air. The combination of the viscosity modifier and agitation suspends the particles, avoids entrapment of air, and achieves an acceptable viscosity to enable good processing / manufacturing conditions, including good pumpability (i.e., the ability to pump the composition from a storage tank into a dipping tank). Ultrasonic treatment can also be used to help release the entrapped air bubbles without causing particle sedimentation.

[0121] In some embodiments where the use of a pseudoplastic viscosity modifier is not particularly required (e.g., for multi-detectable particles (a) and (b) together), the viscosity modifier can be a water-miscible or water-soluble organic polyol, or a water-soluble or water-miscible thickener, examples of which are well known in food or pharmaceutical manufacturing. Examples of viscosity modifiers of natural origin or natural derivation include gums, casein, saccharides, cellulose-based thickeners, clays, and the like. Examples of synthetic viscosity modifiers include acrylic thickeners, alkali-swellable thickeners, wax thickeners, and non-associative thickeners. Combinations of viscosity modifier types such as ASE and polysaccharides can also be used. In embodiments of the present invention, non-associative thickeners are used. Thickeners that impart Newtonian or shear-thickening properties to the composition, such as associative polyurethane thickeners, hydrophobically modified polyether thickeners for Newtonian flow behavior, polyethylene glycol, or propylene glycol, should be avoided as they do not impart the required properties.

[0122] In preferred embodiments and aspects of the invention, regarding the use of a single type of particle (e.g., coated or uncoated magnetite) and a pseudoplastic viscosity modifier, the viscosity modifier must impart pseudoplastic properties to the latex mixture. Examples of pseudoplastic viscosity modifiers include non - associative alkali - swellable emulsion (ASE) type thickeners (e.g., acrylic alkali - swellable emulsion thickeners), polysaccharides such as xanthan gum, and fumed silica. Cellulosic thickeners can be used but are less preferred. Silicates and activated phyllosilicates can be used but are less preferred. ASE thickeners are a known class of materials based on dispersions of acid - functional acrylic polymers in water. One example is Rheovis AS1125, but many others are available. (However, hydrophobically modified ASE thickeners are preferably avoided). The pseudoplastic properties can be measured by preparing a formulation containing the selected viscosity modifier (a dipping formulation containing latex, cross - linker, particles, etc.), measuring the viscosity after 24 hours (Brookfield viscometer, spindle number 3, 30 rpm), and comparing it with the viscosity measured at 60 rpm after 24 hours. If the viscosity is lower at 60 rpm, this indicates pseudoplastic properties. Preferably, the pseudoplastic properties are high pseudoplastic properties. For example, stirring of the composition reduces the measured viscosity of the composition by at least 25% (at 60 rpm compared to 30 rpm), and preferably it is desirable to reduce the measured viscosity of the composition by at least 30% or 40%.

[0123] After 24 hours, when tested using a Brookfield viscometer at 30 rpm with spindle number 3, the viscosity modifier is preferably used in an amount that provides a viscosity of 50 to 1200 centipoise (cps) to the elastomeric film-forming composition. If testing with spindle 3 is not possible, spindle number 1 or 2 can be used. To maintain test consistency, the test should be conducted at a temperature of 25 °C. The most preferred viscosity ranges are 100 - 300, 200 - 1200, 200 - 1000, 250 - 1000, 200 - 500, or 250 - 800, or 500 - 1000, based on the test results shown in Tables 19(a) - 20.

[0124] According to Tables 19(a), 19(b), and 20, the ranges of undesirable values are less than 50 cps and greater than 1600 cps. Nevertheless, in some cases, it may be possible for the viscosity to be less than 50 cps, to rely on continuous stirring to suspend particles during immersion and disperse them throughout the composition, and to obtain a viable product.

[0125] The amount of viscosity modifier can be in the range of 0.1 - 10 phr, for example, 0.5 - 10 phr or 0.5 - 6.0 phr, however, this can vary depending on the choice of viscosity modifier, the viscosity, pH, and temperature of the elastomeric film-forming composition without the modifier. The minimum amount is preferably at least 0.5, 0.75, 1.0, 1.25, 1.5, 1.75, 2.0, 2.25, 2.5, or 2.75 phr. The maximum amount can be 10, 9, 8, 7, 6, or 5 phr. These amounts are particularly suitable for acrylic thickeners such as ASE type thickeners. These amounts are also suitable for polysaccharide thickeners. The amounts can be approximately the same for other types of thickeners and can be adjusted for those that are effective at low concentrations (e.g., HASE type thickeners).

[0126] In some embodiments, the viscosity modifier is filtered from the article in a later stage of article manufacture. For example, in an immersion process, the viscosity modifier can be filtered from the cured article during a washing stage. Nevertheless, some viscosity modifier may remain in the article product, indicating its presence in the composition used to form the product.

[0127] Stabilizers can be used in the elastomeric film-forming composition. The stabilizer can be, for example, an anionic surfactant and / or other nonionic surfactants. The elastomer-forming polymer can be diluted with a solution of a stabilizer such as potassium hydroxide, ammonium hydroxide, and / or sodium hydroxide. The amount of stabilizer used depends on the polymer used in the elastomeric film-forming composition, the pH of the composition, and other factors. The stabilizer can be in the range of 0.1 - 5.0 phr, for example 0.5 - 2 phr, preferably 1.0 - 1.5 phr, and is diluted with water, preferably filtered or deionized water, or water having a total solids level of approximately 5 ppm.

[0128] Emulsifiers can be used in the elastomeric film-forming composition. Suitable emulsifiers include sodium alkylaryl sulfate, sodium alkyl sulfate, or other anionic / nonionic surfactants. The amount of emulsifier used depends on the polymer used in the elastomeric film-forming composition, the pH of the composition, and other factors. The amount of emulsifier can be in the range of about 0.1 - 3 phr.

[0129] A pH stabilizer can be used to avoid the possibility of destabilization that can occur when the polymer contains carboxylic acid groups. Suitable pH stabilizers include potassium hydroxide, ammonium hydroxide, and / or sodium hydroxide. Preferably, the pH stabilizer is potassium hydroxide. The diluted stabilizer solution can be mixed with the polymer. The pH of the mixture is preferably adjusted to about 8.5 - about 12.5, or about 8.5 - about 11.0. Then, a crosslinking agent can be added to the mixture.

[0130] An antioxidant can be added to the elastomeric film-forming composition of the present invention. Suitable antioxidants include hindered arylamines or polymer hindered phenols, as well as Wingstay L (a product of p-cresol and dicyclopentadiene). The antioxidant can be added in an amount in the range of, for example, 0.0 to 5.0 phr, 0.0 to 3.0 phr, 0.0 to 1.0 phr, or 0.3 to 0.5 phr.

[0131] Pigments such as titanium dioxide, which are selected for coloring with pigments or to reduce the transparency of the final elastomeric film, can be added in an amount in the range of 0.01 to 10.0 phr, for example 1.5 to 2.0 phr or 1.0 to 3.0 phr, and colorants can also be added in a desired amount. The mixture is then diluted to the target total solids concentration by the addition of a liquid such as water. The pigments used in the elastomeric film-forming composition can be selected from the group consisting of dyes approved by EN / USFDA.

[0132] A rubber deodorant can be used in the elastomeric film-forming composition. Suitable rubber deodorants include essential oils of natural or synthetic origin. The amount of the rubber deodorant can range from about 0.001 to 2.0 phr.

[0133] A wetting agent can be used in the elastomeric film-forming composition. Suitable wetting agents and emulsifiers include anionic surfactants such as sodium dodecylbenzenesulfonate or sodium lauryl ether sulfate, or nonionic ethoxylated alkylphenols such as octylphenoxypolyethoxyethanol, or other nonionic wetting agents. The amount of the wetting agent can range from about 0.001 to 2.0 phr.

[0134] Defoamers can be used in the elastomeric film-forming composition. The defoamer can be selected from naphthalene-type defoamers, silicone-type defoamers and other non-hydrocarbon-type defoamers, or defoamers of refined oils of plant origin. The amount of the defoamer can be in the range of about 0.001 to 2.0 phr.

[0135] The elastomeric film-forming composition can also be blended with an inorganic filler. Suitable inorganic fillers include titanium calcium carbonate, carbon black, or clay. Preferably, the amount of the inorganic filler contained in the blend does not exceed 75% alone or in combination. It will be recognized that the blended composition retains favorable properties.

[0136] A sensitizer is a chemical substance that can be used to control the amount of the composition that remains coated on the mold during dipping (film deposition) in a composition for generating an elastomeric film. Examples of sensitizers known in the art that can be used in a composition for generating an elastomeric film include polyvinyl methyl ether, polypropylene glycol, ammonium nitrate, and ammonium chloride. The amount is generally 0.01 to 2.0 phr, for example 0.1 to 1.0 phr. When other techniques are used to control the film thickness on the mold, for example when starting with multiple dips of the composition for generating an elastomeric film into a coagulant after pre-dipping the mold in the coagulant, the composition for generating an elastomeric film may not require a sensitizer.

[0137] One skilled in the art will be able to readily vary the components of the elastomeric glove or film-forming composition as appropriate to the situation. Also, one skilled in the art will understand that the specific chemicals or compounds listed above are intended to represent conventional materials that can be used when formulating an elastomeric film-forming composition and are merely intended as non-limiting examples of such components of the composition.

[0138] The elastomer film-forming composition comprises - a step of solubilizing a crosslinking agent that requires solubilization before adding it to the latex composition, - a step of mixing the dispersion of the elastomer with the crosslinking agent, - a step of adding the particles (a(i)), (a(ii)), and / or (b), - a step of adding a viscosity modifier, and subsequently, - a step of homogenizing the viscosity modifier throughout the composition and stirring to distribute the particles (a(i)), (a(ii)), and / or (b) throughout the composition, and - a step of diluting to reduce the total solids content of the formulation and can be prepared thereby.

[0139] The particles (a(i)), (a(ii)), and / or (b) are preferably prepared in advance in a liquid medium that may contain an ionic and / or non-ionic surfactant, a dispersant, etc., which function to prevent aggregation or agglomeration of the particles in the liquid medium. Other additives that can be added to improve the stability of the dispersion are a viscosity modifier, an anti-settling agent, and a water retention agent. Preferably, the latex composition may also have such surfactants, dispersants, and viscosity modifiers to prevent aggregation or agglomeration of the particles in the composition. Examples of anti-settling agents include fumed silica, clay (e.g., organic clay), such as bentonite, polyamide, polyolefin particles, and sulfonates. Examples of water retention agents include glycols, such as propylene glycol, sugar polyols, such as glycerin, and other suitable hygroscopic additives.

[0140] The composition should be continuously stirred during the time the mold is immersed in the composition.

[0141] Preparation of the elastomer article The composition is formed into the shape of a glove and then cured. Curing is used in the general sense to refer to the stage at which cross-linking within the article is achieved. The curing conditions are known to those skilled in the art.

[0142] Any known technique, including dipping processes, extrusion molding, etc., can be used to form the desired shape of the elastomeric article.

[0143] The dipping process involves dipping a former into the composition and curing the composition on the former. The cured product (article) is peeled from the former. Dipping is a process particularly suitable for the manufacture of gloves and finger sacs.

[0144] The steps in the manufacture of gloves using the dipping process are as generally described in PCT / AU2014 / 000726 and PCT / AU2014 / 000727. These patent publications relate to the manufacture of unsupported film products. When making a supported film, adjustments can be introduced into the process, for example, by adding the step of attaching a woven or knitted liner onto the former before dipping into the elastomeric film-forming composition. In such cases, there is an option to use an adhesion dipping process or the adhesion dipping process can be omitted.

[0145] The elastomeric film-forming composition used for dip molding articles such as gloves can, in some embodiments, have a total solids content of about 5 - 50%, for example 5 - 40%. However, the total solids content can be higher. For example, when the article is manufactured by other processes such as extrusion molding or casting, a thermoplastic elastomer can be used and the total solids content can be up to 100%.

[0146] One suitable method for manufacturing a product in the dipping process is - dipping the former into a coagulant containing cationic polyvalent ions, such as a calcium coagulant, to produce a former coated with the coagulant; - A step of immersing a mold coated with a coagulant into the above-described elastomeric film-forming composition containing a viscosity modifier, with stirring and optionally ultrasonic treatment of the elastomeric film-forming composition to maintain the dispersion of the particles in the composition; - Optionally, a step of repeating the immersion step one or more times, with drying or partial drying before each subsequent immersion step; - A step of drying and / or curing the elastomeric film-forming composition to produce an elastomeric article may be included.

[0147] As described above, when a supported film product such as a supported glove is made, the adhesion immersion step in the above process outline may or may not be performed. Further, there is an option to perform this with or without a heat-sensitive agent. A liner (e.g., a woven or knitted liner) may be attached to the mold, which may or may not have a layer of coagulant on its surface (and optionally with or without a heat-sensitive agent), and then the mold with the attached liner is immersed into the elastomeric film-forming composition, followed by performing the other steps described.

[0148] Further details of the basic process steps in some embodiments are as follows.

[0149] Optional step (a) A step of immersing a mold into a coagulant containing polyvalent ions in solution A suitable mold based on the shape of the article to be produced (e.g., flat for a film or glove-shaped for a glove) is immersed in a coagulant containing polyvalent ions in solution. Immersing the mold in the polyvalent ion-containing coagulant leaves a thin coating of charged ions on the surface of the mold. The charged ion coating can assist in controlling the amount of the composition that remains on the surface of the mold after immersion in the composition for forming an elastomeric film through charge interactions. A cationic polyvalent ion-containing coagulant such as a calcium coagulant is typically used. The concentration of polyvalent ions in the coagulant can be roughly in the range of 0.0 to 25 wt% of the coagulant solution (measured as the polyvalent ion compound in the polyvalent ion solution).

[0150] Optional step (b) Drying or partially drying the mold immersed in the coagulant When the mold is immersed in the coagulant, this step is followed by drying or partially drying the mold.

[0151] Step (i) Immersing the mold in the elastomeric film-forming composition to form a layer of the elastomeric film-forming composition on the mold The mold is immersed in the composition for forming an elastomeric film. This aspect has been described in detail above. The immersion period, temperature, and mold surface temperature may be as described in the PCT published patent application mentioned above. When making a supported film, there may be a preliminary step of attaching a liner to the mold.

[0152] Step (ii) Drying or partially drying the layer of the elastomeric film-forming composition on the mold The conditions and details of this process may be as described in the PCT published patent application mentioned above. The manufacturing method described in this specification includes the preparation of single-layer or multi-layer elastomeric films. Thus, in some embodiments, the method can include step (v), which includes drying and curing the laminated elastomeric film on a mold immediately after this step to prepare a single-layer elastomeric film. In other embodiments, the method can include repeating several times the optional steps (iii) and (iv) after this step to produce a multi-layer elastomeric film.

[0153] Step (iii) An optional step of immersing a mold coated with a dry or partially dry layer of an elastomeric film-forming composition into the elastomeric film-forming composition to produce a further layer of the elastomeric film-forming composition on the mold This step is optional and exists when a multi-layer article is produced. The details of this step are as described in the PCT published patent application mentioned above.

[0154] Step (iv) An optional step of optionally repeating the drying or partial drying step (ii) and the further immersion step (iii) This step is optional and exists when a multi-layer article is produced. The number of layers can be two, three, or more in a multi-layer article. The details of this step are as described in the PCT published patent application mentioned above.

[0155] Step (v) An optional additional step before drying and curing Further steps can be performed to fine-tune the manufacture of the elastomeric film or article. The details of these steps are as described in the PCT published patent application mentioned above. Briefly, the film or article can be filtered to remove extractable components, a coating material can be applied, bead / cuff processing can be performed, and / or the product can be passed through a curing or vulcanizing oven to evaporate water in the film and enable better cross-linking.

[0156] Step (vi) drying and / or curing the laminated elastomer film on the former Details of this step are as described in the PCT published publication mentioned above.

[0157] Step (vii) additional steps As additional optional steps that can be carried out before peeling the glove from the former, in any suitable order, there may be mentioned a cooling step, a chlorination step, a post-curing rinse step, a polymer coating step and an additional drying step. Also, the cured film can be cooled / chlorinated / neutralized - post-filtered in hot water and optionally immersed in a lubricant solution or any silicone / silicone-free polymer to allow for easy peeling and better wearing. Any optional coating layer that can be applied may further contain particles of type (a) and / or (b), although this is not particularly desired.

[0158] Step (viii) peeling At the end of the forming process, the film or article is peeled from the former. Optionally, the glove may be turned inside out after peeling, if necessary, to switch the inner layer to the outside.

[0159] Metal detection and X - ray detection An article of an aspect of the present invention, or a small volume portion thereof (e.g., at least about 0.05 mm 3 , e.g., about 0.08 mm 3 , or another portion sized 0.05 - 1.0 mm 3 or any size greater than 1.0 mm 3 ), due to the presence of particles of type (b), is detectable by a metal detector and an X-ray detector even in the presence of background metal. The detectable portion has a size of about 0.08, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 2.0, or 5.0 mm 3It is possible. The detectable volume may be converted to a specific area (based on the film thickness). For a film having a thickness of 0.01 to 2 mm, about 0.03 mm 2 ~100 mm 2 A portion of the film having an area of is preferably detectable. The detectable portion of the film in this thickness range has an area of about 0.05, 0.08, 0.1, 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, or 500 mm 2 in size. A metal detector suitable for detecting the presence of an article or a portion thereof is the Anritsu Duw-M5 Series KDB3005AHF Metal Detector System, which has a detection sensitivity for an iron ball having a diameter of 0.5 mm. A suitable X-ray detector is the Anritsu KD74 Series KD7416DWH X-ray inspection system.

[0160] Any article (or a portion thereof) that generates a signal output indicating the presence of metal in a metal detector, such as the metal detector systems specified herein, is considered to be metal detectable. The signal output can be audible, visual, or otherwise, depending on the type of metal detector used. An article (or a portion thereof) that generates a signal output in an X-ray detector that is greater than the baseline signal based on a comparative article sample that does not contain particles (a) and (b) is considered to be X-ray detectable. (In the examples, a glove manufactured from formulation B that does not contain particles (a) and (b) was used as the comparative article sample for setting the baseline. This formulation can be used to set a comparative article sample for the purpose of determining X-ray detectability when other comparative article samples cannot be determined). Preferably, the article (or a portion thereof) is X-ray detectable relative to the baseline of an aluminum foil having a thickness of 0.06 mm. In some embodiments, the article (or a portion thereof) has higher X-ray detectability and is X-ray detectable relative to the baseline of an aluminum foil having a thickness of 0.09 mm. In some cases, the size of the portion is as described above. It is noted that only a very small portion of the article can be detected by such detectors.

[0161] The inclusion of particles (a(i)) and (b) in the articles of the embodiments of the present invention has been found to improve migration test results compared to a similar comparative product of the same thickness that does not contain particles (a) and (b). In some embodiments, the articles have a migration test result of less than 10 mg / dm3 when measured against a 50% ethanol:water mixture according to EN standard EN1186. 2 In some embodiments, the migration test result is less than 9 mg / dm 2 Less than 8 mg / dm 2 Less than 7 mg / dm 2 Less than or equal to 6 mg / dm 2 Migration test results show that thinner gloves are less than 4.0 mg / dm 2 It may even be less than 100%. This test is an indication of the migration of soluble and insoluble components of the article (glove) into food, or the equivalent based on the test. For articles intended for contact with food, it is important to have low migration results, and it has been found that the articles of the present invention meet this requirement.

[0162] In the claims and the foregoing description, unless the context otherwise requires, either by express language or necessary implication, the term "comprises" or variations of "comprises" or "comprising" are used in a non-exclusive sense, i.e., used to specify the presence of stated features in various aspects of the invention, but not to exclude the presence or addition of further features. Moreover, unless the context indicates otherwise, a reference to "a" specified feature should be construed as a reference to one or more specified features. Thus, "a viscosity modifier" refers to the presence of one or more such viscosity modifiers. EXAMPLES

[0163] The present invention will now be described in more detail with reference to the following non-limiting examples involving the preparation of elastomeric film gloves.

[0164] General procedures for the production of elastomeric gloves In the examples described below, unless otherwise indicated to the contrary, elastomeric gloves were produced using the following general procedures.

[0165] 1. Preparation of the crosslinkable composition For these examples involving a crosslinkable composition, it was prepared as follows. One part of sodium aluminate as the selected polyvalent metal source was mixed with one part of sodium hydroxide and one part of potassium hydroxide as alkalis and one part of glycerin as a stabilizer in six parts of water. Then, one part of this first concentrate was mixed with ten parts of water to produce a crosslinkable composition containing 96 parts of water and one part each of sodium aluminate, NaOH, KOH, and glycerin. The mixture was heated at a high temperature (typically around 95 °C, but it could be any temperature from 80 °C to the boiling point) to dissolve the polyvalent metal by forming negatively charged polyvalent metal complex ions. The concentration of metal ions in the resulting crosslinkable composition was 0.66 wt% or 0.33 wt% of the total solution, respectively. The pH of the solution was in the range of about 12 - 13.

[0166] 2. Preparation of the latex composition The elastomeric film-forming composition is prepared from selected nitrile latex and other components as described in the specific examples below. Some examples contained the crosslinkable composition described in step 1, and some did not. The latex formulations for producing specific layers of the film contain particles (a(i)), (a(ii)), or (b), or combinations thereof. The steps involved in formulating the latex were - Incorporating the crosslinkable composition as in step 1 above (when present in the latex formulation), - Mixing a dispersion of the elastomer with a crosslinking agent containing any sulfur and accelerator (and, when used, the solubilized ionic crosslinking agent of step 1), followed by - adding particles (a(i)) and / or (a(ii)) and / or (b), followed by - adding a viscosity modifier, followed by - homogenizing the viscosity modifier throughout the composition and stirring to distribute particles (a(i)) and / or (a(ii)) and / or (b) throughout the composition, and - diluting to reduce the total solids of the formulation was included.

[0167] 3. Washing After removing the glove already made on the mold, the mold is subjected to pre-washing to wash away the residue. The mold is washed in weak acid / weak alkali and hot water. Next, the mold is dried by blowing air with a blower or an air curtain, or by using an oven with hot air having a temperature above 105 °C.

[0168] 4. Coagulation Immersion The washed and dried mold is immersed in a coagulant bath containing a 0-50 wt% solution of calcium nitrate. The coagulant also contains a wetting agent (0.001-1.0%) and an antifoaming agent (0.001-1.0%). In some embodiments, coagulation immersion is not required. In the examples carried out herein, the coagulant contained 7-15% calcium nitrate.

[0169] 5. Immersion Process The mold coated with the dry coagulant is immersed in a tank containing the latex composition described in Step 2 above. The composition is maintained at a temperature of approximately 20-35 °C and constantly circulated in the tank. Ultrasonic treatment may be used to avoid bubbles.

[0170] 6. Drying The mold coated with the composition is gelled in a gelling oven at a temperature of about 80-300 °C and a duration of 2-300 seconds.

[0171] 7. Prefiltration This step is optional. The pre-filtration was completed after the final immersion into the latex composition followed by gelation. The pre-filtration is carried out by rinsing briefly in warm water. The gelled film coating on the former is pre-filtered at any temperature between ambient temperature and 95 °C in a series of tanks. In the examples, it was typically about 55 °C.

[0172] 8. Second immersion step This step is optional and is carried out when a further layer of the elastomeric film is to be formed on top of the first layer of the elastomeric film-forming composition. This step may optionally involve an additional adhesion immersion into a coagulant composition, such as a coagulant composition containing 1-10% calcium nitrate, before the second immersion is carried out. An additional adhesion immersion may be advantageous if a significant amount of particles (a(i)) and / or (a(ii)) and / or (b) are present in the second layer of the elastomeric film-forming composition. It is also used to produce a second layer having a similar thickness or a greater thickness compared to the first layer.

[0173] 9. Gelation / pre-filtration / bead processing This pre-filtration step is optional and, in the case of multiple immersions of the latex composition, is carried out in this order after a further layer of the elastomeric film has been formed. The product after the second immersion step is subjected to gelation and pre-filtration and bead processing. In the case of an online polymer coating, the order is gelation / pre-filtration / polymer coating / bead processing.

[0174] In the case of a single immersion of the elastomer, the pre-filtration is completed as described above. The product after the immersion step is subjected to gelation and pre-filtration and bead processing. In the case of an online polymer coating, the order is gelation / pre-filtration / polymer coating / bead processing.

[0175] The bead processing step, the drying step, and the pre-filtration step can be carried out in any order. Depending on the quality of the cuff bead processing, the processes of bead processing and pre-filtration before curing may be interchanged.

[0176] 10. Curing Curing was carried out at about 80 °C to 150 °C for about 15 to 30 minutes, depending on the film thickness and the intended final product properties.

[0177] 11. Post - filtration / Lubricant / Final Drying / Release / Tumbling In the case of glove products, the cured elastomeric articles may be subjected to one or more process steps including post - filtration, chlorination (note that this can alternatively be done prior to curing), neutralization, additional curing / surface treatment and / or lubricant application (e.g., by immersion into a lubricant composition).

[0178] Test procedures For all of the examples, tests were conducted to determine the following properties of the film. · Modulus at 100%, 300%, and / or 500% elongation; · Tensile strength (MPa / Psi) (1 MPa = 145 Psi); · Elongation (%); and · Breaking point load (N).

[0179] Tensile strength, stress at 100%, 300%, and / or 500% modulus, and elongation at break were measured by test methods conducted in accordance with ASTM D 412 - 06a (2013) based on the sample size set by the criteria for gloves. The gloves were also tested for the breaking point load (or force at break) measured in accordance with EN 455. The criteria are readily available. These tests can be applied to multilayer films and gloves (e.g., examination gloves for medical use). In all result tables, the values shown for tensile strength and modulus are in units of MPa, the values shown for breaking point load are in units of N, and the values shown for elongation (or elongation at break) are in units of %.

[0180] General formulation Typical formulations for three different compositions containing different polymer latex types are as follows.

[0181] (Table 1) TIFF0007691364000001.tif102151

[0182] The reference to the amount of the above phr of the crosslinkable composition relates to the amount of each of the trivalent metal source and the hydroxide based on phr per 100 parts of the nitrile polymer.

[0183] (Table 2) TIFF0007691364000002.tif111151

[0184] (Table 3) TIFF0007691364000003.tif111151

[0185] Example 1 The particle blend was prepared as follows.

[0186] (Table 4) TIFF0007691364000004.tif58151

[0187] In the examples demonstrated herein, the particles of type (a(i)) were magnetite particles having a mass average particle size of 0.8 μm (D50) for MDP1 to MDP5, and coated iron particles having a mass average particle size of 1.5 μm (D50) for DP6 and DP7. The particles of type (a(ii)) were coated aluminum particles having a mass average particle size of 11 μm (D50), and the particles of type (b) were tungsten or bismuth oxide particles having a mass average particle size of 1.5 μm (D50). Tungsten particles were used in Examples 1, 2, and 8, while bismuth oxide was used in Examples 3, 4, 5, 6, and 7.

[0188] Seven formulations were prepared for use in different combinations to produce articles having different layer (s) arrangements and particle compositions as follows.

[0189] Formulation A: For the production of a metallic gray layer having a multi-detectable particle blend of (a(i)) and (b) based on MDP 1.

[0190] (Table 5) TIFF0007691364000005.tif123128Viscosity at 25 °C, spindle 3, 30 rpm: 332 cps.

[0191] Further formulations were produced having the same components listed above but with lesser amounts of viscosity modifier and pH adjuster (4.0 and 0.4 phr respectively).

[0192] Formulation B: For the production of a blue-toned layer without particles (a(i)), (a(ii)), and (b).

[0193] (Table 6) TIFF0007691364000006.tif84128

[0194] Formulation C: For the production of a metallic gray layer containing a multi-detectable particle blend of (a(i)) and (b) based on MDP 2.

[0195] (Table 7) TIFF0007691364000007.tif97128Viscosity at 25 °C, spindle 3, 30 rpm: 372 cps.

[0196] Further formulations were produced having the same components listed above but with lesser amounts of viscosity modifier and pH adjuster (4.0 and 0.4 phr respectively).

[0197] Regarding the generation of a metallic gray layer containing the multi-detectable particle blends of (a(i)) and (b) based on Complex D: MDP 3.

[0198] (Table 8) TIFF0007691364000008.tif Viscosity at 9712825 °C, spindle 3, 30 rpm: 416 cps.

[0199] A formulation having the same components listed above but with a lesser amount of viscosity modifier and pH adjuster (4.5 and 0.5 phr respectively) was further produced.

[0200] Regarding the generation of a metallic gray layer containing the multi-detectable particle blends of (a(i)) and (b) based on Complex E: MDP 5.

[0201] (Table 9) TIFF0007691364000009.tif Viscosity at 9712825 °C, spindle 3, 30 rpm: 416 cps.

[0202] A formulation having the same components listed above but with a lesser amount of viscosity modifier and pH adjuster (4.5 and 0.5 phr respectively) was further produced.

[0203] Regarding the generation of a blue layer containing coated metal-detectable particles (a(i)) based on Complex F: DP 6.

[0204] (Table 10) TIFF0007691364000010.tif Viscosity at 7712825 °C, spindle 3, 30 rpm: 416 cps.

[0205] Regarding the generation of a blue polychloroprene rubber layer containing coated metal-detectable particles (a(i)) and (a(ii)) based on Complex G: DP 7.

[0206] (Table 11) TIFF0007691364000011.tif Viscosity at 10612825 °C and spindle 3, 30 rpm: 476 cps.

[0207] Using the seven formulations above, or variations thereof, the following layer combinations can be prepared. Sample gloves were manufactured based on some of the combinations listed below and subjected to testing. The results of these tests are further shown below.

[0208] (Table 12) TIFF0007691364000012.tif 37158 TIFF0007691364000013.tif 211158

[0209] The appearance or final color of the glove may be determined by the layer arrangement. Since it is known that magnetic particles impart a solid color to the elastomer layer, pigments can be added to layers in which magnetic particles are present in small amounts or not at all. Thus, the elastomeric article can be manufactured in any color other than metallic gray, depending on the intended appearance.

[0210] Gloves were manufactured as follows from Formulations A, B, C, D, E, F, and / or G.

[0211] (Table 13) TIFF0007691364000014.tif 98164

[0212] The properties of the multi-detectable gloves manufactured as such were tested and the results are shown below.

[0213] (Table 14) TIFF0007691364000015.tif 100164

[0214] 100 mm of Films I - V 2The captured X-ray images of the samples are provided as Figure 2. All X-ray images were generated by the Anritsu KXS7534AVCLE X-ray inspection system. In the X-ray images, the areas where the X-ray beam was attenuated appear darker. The order of the films shown in this figure is, from left to right, I, III, IV, V, and II. Glove type II is virtually undetectable by this X-ray imaging, despite being thicker than 50%. Figure 3 is an X-ray image of the same rectangular films (I, III, IV, and V from left to right), with a square of aluminum foil of the same size placed as the last of the imaged squares. This shows that glove types I and III, which have the highest amount of particles (b), are the darkest (most easily detectable), and the darkness decreases as the amount of particles (b) decreases. Figure 4 shows the same X-ray image as in Figure 3, and the corresponding graph below the X-ray image shows the detection intensity (Y-axis peak) compared to a 0.12 mm thick aluminum film. Film V had a lower intensity compared to the aluminum film, while films I, III, and IV had higher intensities (these films I, III, and IV are detectable when using the 0.12 mm thick aluminum film as the baseline). Films I and III had detection intensities that exceeded the threshold level marked by the horizontal line on the graph.

[0215] The properties of metal-detectable gloves (containing magnetic particles alone or in combination with highly conductive particles) were tested, and the results are shown below.

[0216] (Table 15) TIFF0007691364000016.tif52128

[0217] Considering that even a 0.1 mm thick glove having 2.6 wt% of those particles was metal detectable, the amount of particles (a(i)) can be about 1 wt% or more, or 2.0 wt% or more of the glove. Amounts of at least 5, 8, 10, 13, and 20 wt% improve detectability by the metal detector. The amount of particles (a(ii)) is desirably more than 10.0 wt%, preferably at least 14, 17, or 20 wt% in order to provide metal detectability. The amount of particles (b) is desirably more than about 2.7 wt% based on the test data in order to provide X-ray detectability. The amount is preferably at least 7 wt%, 10 wt% or at least 12 wt%, or at least 13.5 wt%. The amounts can vary for products with different film thicknesses, but these numerical values provide an executable range.

[0218] Example 2 Note that the type IV film tested in Example 1 is detectable by X-ray beyond the baselines of three different thicknesses of aluminum foil. To investigate the extent to which the viscosity modifier affects the detectability of the film, the tests were conducted as follows.

[0219] In this example, a modified type of film IV (referred to as IV(a)) having the same formulation as film IV but with the viscosity modifier removed was prepared. The thickness of the produced film was the same. The properties of film IV(a) were examined and tabulated against the properties of film IV in the table below.

[0220] (Table 16) TIFF0007691364000017.tif99138

[0221] It was remarkable and noteworthy that the presence of the viscosity modifier had a significant impact on the detectability of the glove by both metal detection and X-ray detection.

[0222] Example 3 In Example 3, to explore the influence of changing the class of viscosity modifier, the type of elastomer, and the combination of crosslinking agents, tests were conducted on two different latex formulations (different elastomer and crosslinking agent combinations) using two different viscosity modifiers.

[0223] The viscosity modifiers tested were of the following classes. a. An alkali-swellable emulsion (ASE) type thickener that is a dispersion of an acid-functional acrylic polymer in water (i.e., the pseudoplastic acrylic emulsion thickener used in Example 1), for example, Rheovis AS1125. b. A polysaccharide having the same main chain structure as that of cellulose, for example, xanthan gum.

[0224] The elastomer and crosslinking agent combinations tested were of the following classes. i. A nitrile latex containing sodium aluminate, sulfur, and ZDBC. ii. A natural rubber latex containing ZnO, sulfur, and ZDBC.

[0225] Formulations containing various amounts and identities of viscosity modifiers (their amounts and identities are shown in the table following the formulation table) were manufactured and tested. The viscosity of each formulation was tested at 25 °C using a Brookfield viscometer at 30 rpm with spindle No. 3. The viscosity was further tested under the same conditions but at a spindle speed of 60 rpm or using a different spindle, where the viscosity was such that the different spindles were justified.

[0226] (Table 17) TIFF0007691364000018.tif95128

[0227] (Table 18) TIFF0007691364000019.tif86128

[0228] (Table 19(a)) TIFF0007691364000020.tif99156

[0229] (Table 19(b)) TIFF0007691364000021.tif89157

[0230] (Table 20) Natural rubber latex compound TIFF0007691364000022.tif76160

[0231] Good quality nitrile gloves having a sufficiently uniform distribution of MDP particles can be manufactured using 3.3, 3.5 phr, 4.0 phr, 4.5 phr, and 5.0 phr of ASE type thickeners or 1.0, 1.5, 2.0, 2.5, 3.5, or 4.0 phr of polysaccharide type thickeners, provided that the dipping was carried out within an appropriate period (i.e., before precipitation as indicated in the comments). Good quality natural rubber latex gloves having a sufficiently uniform distribution of MDP particles could also be manufactured using about 1.0, 1.5, 2.5, or 4.0 phr of polysaccharide thickeners.

[0232] All thickeners imparted pseudoplastic properties to the dipping formulation. As an example, 5.0 phr of an ASE thickener gave a viscosity of 1084 cps at 30 rpm, which decreased by 36% to 639.9 cps after stirring at 60 rpm. Polysaccharide thickeners generally have a greater effect on viscosity increase at lower dosages compared to ASE-type thickeners, and as a result, it is more difficult to control viscosity by dosage compared to ASE-type thickeners. Based on the viscosities obtained at 30 rpm (spindle numbers 1, 2, and 3), the preferred viscosity range is 50 - 1200 centipoise. For nitrile latex, it is most desirable to select a viscosity modifier and the amount to be used based on achieving a viscosity at 30 rpm (spindle number 3) of about 250 - 1000, preferably 250 - 500 centipoise. A viscosity within the range of about 250 - 1000 is preferred because the composition was successfully stabilized and ensured a complete distribution of particles throughout the composition. Based on this, for nitrile gloves, approximately 4.5 and 3.5 phr of ASE-type and polysaccharide-type thickeners, respectively, gave the best results for compositions having 15% TSC. For natural rubber latex, the amount of polysaccharide thickener is preferably about 2.0 - 4.0 phr. Note that changing the total solids affects the amount of thickener most suitable for achieving the desired viscosity level. The total solids of the formulations in Tables 17 and 18 were 15%.

[0233] Example 4 Formulation H containing multi-detectable particles was prepared and used to manufacture double-layer and single-layer gloves designated as Gloves VIII and IX, respectively. The magnetite particles had an average particle size as shown for the previous examples, and the bismuth oxide particles had an average particle diameter (D50) of 1.6 μm. The physical properties of the gloves were tested and the test results are shown below.

[0234] Formulation H: For the production of a metallic gray layer containing a blend of multi-detectable particles of (a(i)) and (b) based on MDP 4.

[0235] (Table 21) TIFF0007691364000023.tif Viscosity at 25°C, spindle 3, 30 rpm: 476 cps.

[0236] Formulations having the same components listed above but with a lesser amount of viscosity modifier and pH adjuster (4.5 and 0.5 phr, respectively) were further produced.

[0237] Gloves were manufactured from formulation H according to the following parameters.

[0238] (Table 22) TIFF0007691364000024.tif 33134

[0239] The physical properties of the gloves were as follows.

[0240] (Table 23) TIFF0007691364000025.tif 104164

[0241] Note that detectability was measured against different “baselines” including: (a) a baseline of a formulation containing no detectable particles (i.e., gloves made from formulation B as the baseline), and (b) baselines of three different thicknesses of aluminum foil. Gloves of types VIII and IX have a high filler loading of 30 phr, and both gloves can provide good physical properties despite the high loading and low thickness.

[0242] This example demonstrates that an article, and in particular a glove, can be manufactured with a sufficiently high detectability (even based on a low test sample / a part size) while remaining very thin in order to provide a sufficiently high tactile sensitivity when worn by a user. This example demonstrates the effective manufacture of very thin (approximately 0.04 mm thick) gloves that are still detectable even with a low part area size. The thinness and tactile sensitivity are important features to ensure that the gloves are accepted by consumers / in the workplace. Achieving a balance between the high detectability of the gloves and their low thickness and good tactile properties (strength, modulus) was an important achievement.

[0243] Example 5 Double - layer gloves were manufactured from formulation I and compared with gloves of type VIII described above manufactured from formulation H. Formulation I was prepared as follows.

[0244] (Table 24) TIFF0007691364000026.tif106133

[0245] The viscosity modifier was present in formulation I in an amount that provided a latex composition with a total solids of 15% and a viscosity of 480 cps (at spindle 3, 30 rpm). The original version of the formulation used for previous test studies is designated as variant (i). A modified version was also prepared with a smaller amount of the cross - linking agents ZnO and ZDBC, which is designated as variant (ii). Variant 2 had a slightly lower viscosity than variant (i) due to the smaller amount of viscosity modifier.

[0246] Gloves designated as type X were manufactured from formulation I (using two variants for the formulation and thus further designated as X(i) and X(ii)). The properties were tested and compared with the properties of glove type VIII manufactured from formulation H. The properties are summarized in the table below.

[0247] (Table 25) TIFF0007691364000027.tif137139

[0248] Table 25 shows different formulations that support similar phr loadings of detectable particles (a) and (b). Both films were of the same thickness. The crosslinker combination (and also the amount used) differed between the formulations, but the results indicate that, despite this difference, the overall glove properties were good. Glove type X (both variants (i) and (ii)) had a lower elongation at break than glove type VIII, but was still within the acceptable range, and the tensile strength was similar between the products. Both were detectable by metal and X-ray at a minimum volume of 1.0 mm 3 and were detectable by metal and X-ray at a minimum volume of 1.0 mm

[0249] Example 6 Gloves manufactured according to the formulations of the examples with detectable particles (a) and (b) are expected to come into contact with various surfaces in standard use and may in particular come into contact with food. For this reason, tests were carried out on the tendency for migration of soluble or insoluble substances in the gloves to occur. The overall migration limit of the gloves is described in this example. A formulation J containing multi-detectable particles was prepared and used to manufacture single-layer and double-layer gloves according to the above-described procedure, designated glove XI and glove XII, respectively.

[0250] For formulation J: Regarding the production of a metallic gray layer containing a blend of multi-detectable particles of (a(i)) and (b) based on MDP 3.

[0251] (Table 26) TIFF0007691364000028.tif100128

[0252] Gloves were manufactured from formulation J and control gloves were prepared from formulation B according to the following parameters.

[0253] (Table 27) Properties of the compositions for each glove type TIFF0007691364000029.tif36128

[0254] (Table 28) Physical properties for each handbag type TIFF0007691364000030.tif39128

[0255] The overall migration test was carried out on M-sized gloves according to standard EN 1186 using 50% ethanol as a food simulant. The overall migration values of the prepared gloves were as follows.

[0256] (Table 29) TIFF0007691364000031.tif54164

[0257] Table 29 shows the overall migration values, indicating that all the gloves tested were below the overall migration limit of 10 mg / dm 2 . Interestingly, it was found that the migration of soluble or insoluble substances decreased by adding detectable fillers to the gloves. The detectable particles not only showed no specific tendency to migrate out of the glove product, but they were also assumed to function as a barrier limiting the tendency of other soluble or insoluble substances in the glove to migrate out. For gloves having the same thickness as the control gloves, the migration levels were lower, which is the positive additional effect of including particles (a) and (b) in the gloves. The thicker glove, glove type XII, produced higher migration than glove type XI and the control gloves because the amount of substance extracted was higher compared to the thinner gloves. Nevertheless, despite having a thickness more than twice as thick, the migration was only slightly greater than that of the control gloves.

[0258] Gloves were further manufactured using additional variations for formulation J with further reduced amounts of viscosity modifier (3.0 phr) and pH modifier (0.3 phr).

[0259] Example 7 - Radiation attenuation Gloves manufactured according to the formulations of the examples (excluding comparative examples) have radiation attenuation properties. This provides an additional function to the gloves.

[0260] The radiation attenuation characteristics of the gloves can be tested in accordance with EN 61331-1.

[0261] A formulation K containing multi-detectable particles was prepared at a total solids content of 40% and used to produce a double layer designated glove type XIII, which was tested in accordance with EN 61331-1. Formulation K was used to produce gloves in this manner at a higher total solids content than for the previous example, producing thicker gloves suitable for use in radiation attenuation applications. For such gloves, a second adhesion dip may also be performed after the production of the first dip layer of the elastomeric film-forming composition and before the second dip into the composition to achieve the desired thickness.

[0262] The physical properties and test results of the gloves are shown below, thereby comparing glove type XIII with control gloves produced in accordance with formulation B.

[0263] For formulation K: regarding the production of a metallic gray layer containing a multi-detectable particle blend of (a(i)) and (b) based on MDP 2.

[0264] (Table 30) TIFF0007691364000032.tif97128

[0265] (Table 31) Characteristics of the compositions for each glove type TIFF0007691364000033.tif23128

[0266] (Table 32) Physical properties for each glove type TIFF0007691364000034.tif33164

[0267] (Table 33) Test results for each glove type TIFF0007691364000035.tif33128

[0268] Table 33 shows the attenuation rates at different X-ray intensities of 70 kV and 100 kV, whereby a higher radiation intensity usually shows a lower attenuation rate value. The multi-detectable glove type XIII had a greater tendency to attenuate radiation compared to the control glove, despite having a similar thickness. The presence of particles (b) enables a higher degree of radiation attenuation, while the presence of particles (a(i)) enables metal detection.

[0269] Example 8 Two forms of conductive particles were tested and comparative tests were conducted to evaluate their usefulness (i.e., metal detector detectability) for use in the manufacture of detectable articles. Additional studies were conducted to predict the performance of another type of conductive particle (tin particles) compared to the two studied examples.

[0270] Based on formulation B, but without an opacifier and a blue pigment, and with the addition of a viscosity modifier (pseudoplastic acrylic emulsion 2 phr) and conductive particles according to Table 34 below, two nitrile films were produced using a standard nitrile film formulation.

[0271] (Table 34) Characteristics of nitrile films containing 67 wt% conductive particles TIFF0007691364000036.tif29159

[0272] Gloves were manufactured from two film-forming compositions of types A and B using conventional dipping techniques. Samples were cut from gloves of types A and B having volumes of 40 mm 3 and 400 mm 3 respectively. Film A contained particles of aluminum having a conductivity of 3.77×10 7 S / m, and film B contained tungsten having a conductivity of 1.79×10 7 S / m. Both materials had a density of approximately 0.9×10 7It is more conductive than tin having an electrical conductivity of S / m. It has been found that film A containing more conductive aluminum particles is metal detectable. Film B containing lower conductivity tungsten particles was not detectable in the metal detector test despite a high particle loading (by weight %) and the high film volume tested.

[0273] The high density of tungsten (19.25 g / cm 3 ) results in a smaller volume incorporated into the film based on the same weight % of particles incorporated into the film (based on the total weight of the film) compared to aluminum (2.7 g / cm 3 ). Considering the density of metallic tin (7.27 g / cm 3 ), as well as the density of each of films A and B (the density of the particle-loaded films A and B calculated by reference to the volume and weight of films A and B), and the volume of particles present in each film, an estimate of the metallic tin particle content in a 50 mm 3 film is made and shown in Table 35 below.

[0274] (Table 35) Predicted properties of a film containing 67 wt% metallic tin TIFF0007691364000037.tif24130

[0275] It is noted that when making the above prediction for a film containing 67% metallic tin, the film density of the metallic tin-containing film (based on the same polymer used for films A and B) is thought to be somewhere between those for films A and B, because aluminum and tungsten are at opposite ends of the spectrum for metal density and tin has a density between aluminum and tungsten.

[0276] The films of the present application (see, for example, the films of type I and IV in Table 14) are 5.0 mm mm 3 and 1.0 mm 3The detectability was demonstrated for such a low volume. Based on a loading of 67% by weight, 50 mm 3 The amount of metallic tin (by volume) in the film is estimated to be less than the tungsten content (by volume) in film type B having a size of 400 mm 3 . Since tungsten is known to be more conductive than metallic tin, it is also speculated that glove fragments containing 67% by weight of metallic tin are not detectable (similar to the tungsten example subjected to the tests outlined above). This is in contrast to the small volumes of films of types I and IV outlined in Table 14 which are shown to be metal detectable. The prediction outlined above indicates that a film volume larger than 50 mm 3 is required before fragments of a film containing 67% by weight of tin are detectable by a metal detector. This is a very high minimum value and exceeds the limits required for the metal detectability required herein. 3 Based on this data, the Applicant speculated that for conductive particles to provide an effective means of metal detectability (either alone or in combination with magnetic particles), the conductive particles must have a high conductivity. The conductive particles must both have a conductivity of at least 3×10

[0277] S / m or an electrical resistivity of less than 3×10 7 Ω.m, measured at 20 °C. It is noted that particles having magnetic properties in combination with a conductivity lower than this conductivity minimum may be selected for use in an elastomeric article for (rather than conductivity properties) magnetic properties. An example is iron having a conductivity of 1×10 -8 S / m which can be used as a magnetic particulate material. 7 Without departing from the spirit and scope of the present invention, various modifications can be made to the embodiments described.

[0278]

[0279] Example 9 ​A comparative test was conducted to observe the performance of the corrosion inhibitor on corrosive magnetic particles. Two forms of an iron particle dispersion of the same amount were prepared at 60% total solids. These samples were treated with dilute acetic acid (3%) to promote oxidation and exposed to an ambient temperature of 27 °C and a humidity of 50%. The experiment was conducted for one week to observe the corrosion tendency.

[0280] (Table 36) Observation of Coated and Uncoated Iron Particles after Acetic Acid Treatment TIFF0007691364000038.tif60157

[0281] From Table 36, it is shown that uncoated iron particles in the presence of moisture and oxygen tend to rust. The acidic environment acts as a catalyst and promotes the formation of iron oxide on the surface of the iron particles. The coating on the iron serves as a barrier and minimizes oxidation.

[0282] Example 10 Compound L was prepared as follows.

[0283] (Table 37) TIFF0007691364000039.tif112128

[0284] The viscosity modifier was present in Compound L in an amount that provided a viscosity of 252 cps (spindle 2, 30 rpm) to the latex composition at 20% total solids.

[0285] Gloves of type XIV were manufactured from Compounds B and L and their properties were tested. The properties are summarized in the following table.

[0286] (Table 38) Physical Properties of Gloves of Type XIV TIFF0007691364000040.tif38164

[0287] (Table 39) Test Results of Gloves of Type XIV TIFF0007691364000041.tif99128

[0288] Table 39 shows the characteristics of glove type XIV, which has good tensile strength while having a very excellent elongation at break of 700%.

Claims

1. An elastomeric article comprising an elastomeric film containing one or more film layers, wherein at least one film layer is - The following: (a(i)) Magnetic particles, (a(ii)) At least 3.0×10 7 conductive particles having an electrical conductivity of S / m at 20°C, and / or (b) Particles containing one or more high atomic mass elements having an atomic mass of at least 132, dispersed throughout the film layer Selected from at least one type of particle, and - A pseudoplastic viscosity modifier for achieving dispersion of the particles throughout the film layer The elastomeric article comprising.

2. The elastomeric article according to claim 1, comprising the magnetic particles.

3. The elastomeric article according to claim 2, wherein the magnetic particles have an average particle size based on a mass average diameter of less than 5 μm.

4. The elastomeric article according to claim 2 or 3, wherein the magnetic particles are ferromagnetic particles.

5. The elastomeric article according to claim 4, wherein the magnetic particles are magnetite particles.

6. The elastomeric article according to any one of claims 2 to 5, wherein the magnetic particles are coated with a corrosion inhibitor.

7. The elastomeric article according to any one of claims 2 to 6, wherein at least one film layer comprises the particles containing one or more high atomic mass elements having an atomic mass of at least 132, dispersed throughout the film layer.

8. 5.0 mm 3 The elastomeric article according to any one of claims 1 to 7, wherein a portion of the article is detectable by a metal detector.

9. The elastomeric article according to any one of claims 1 to 8, having a thickness in the range of 0.01 mm to 3 mm.

10. The elastomeric article according to any one of claims 1 to 9, having a modulus at 500% elongation of 1.0 to 25 MPa when measured in accordance with ASTM D 412-06a (2013).

11. The elastomeric article according to any one of claims 1 to 10, having an elongation at break of at least 100% when measured in accordance with ASTM D 412-06a (2013).

12. The elastomeric article according to any one of claims 1 to 11, wherein the total amount of the particles is in the range of 2.0% to 80% by weight of the article.

13. The elastomer is selected from the group consisting of carboxylated or non-carboxylated polyacrylonitrile butadiene, natural rubber, polyvinyl chloride, carboxylated or non-carboxylated polychloroprene, silicone rubber, polyurethane, synthetic polyisoprene, styrene-butadiene, thermoplastic elastomer, polybutadiene, and combinations or copolymers thereof, or is a rubber containing a halide substituent, nitrile rubber, polyurethane, polyisoprene, polychloroprene, acrylic polymer, or a modified polymer or copolymer of polybutadiene, the elastomeric article according to any one of claims 1 to 12.

14. The elastomeric article according to any one of claims 1 to 13, wherein the pseudoplastic viscosity modifier is a non-associative thickener.

15. An immersed elastomeric article, wherein each of the one or more film layers is formed by immersing a forming tool in an elastomeric film-forming composition containing a crosslinking agent and having a total solids content of 5 to 50% so as to produce the elastomeric film having a thickness in the range of 0.01 to 2 mm, the elastomeric article according to any one of claims 1 to 14.

16. - The following: (a(i)) Magnetic particles, (a(ii)) At least 3.0×10 at 20 °C 7 Conductive particles having an electrical conductivity of S / m, and / or (b) Particles containing one or more high atomic mass elements having an atomic mass of at least 132 At least one type of particle selected from, and - A pseudoplastic viscosity modifier for dispersing the particles throughout the elastomeric film-forming composition An elastomeric film-forming composition comprising.

17. The elastomeric film-forming composition according to claim 16, comprising the magnetic particles, and the magnetic particles having an average particle size based on an average diameter of less than 5 μm.

18. The elastomeric film-forming composition according to claim 17, wherein the magnetic particles are coated with a corrosion inhibitor.

19. The elastomeric film-forming composition according to any one of claims 16 to 18, further comprising the particles containing one or more high atomic mass elements having an atomic mass of at least 132.

20. A method for the manufacture of an elastomeric article according to any one of claims 1 to 15, comprising - The following: (a(i)) Magnetic particles, (a(ii)) At least 3.0×10 at 20 °C 7 Conductive particles having an electrical conductivity of S / m, and / or (b) Particles containing one or more high atomic mass elements having an atomic mass of at least 132 mixing at least one type of particle selected from: with a pseudoplastic viscosity modifier into the composition such that the particles are dispersed throughout the elastomeric article forming composition; - immersing a forming tool into the elastomeric film forming composition; and - drying and / or curing the elastomeric film forming composition on the forming tool to produce an elastomeric article The method as described above.

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