US20200199311A1 - Detectable and multi detectable articles - Google Patents

Detectable and multi detectable articles Download PDF

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Publication number
US20200199311A1
US20200199311A1 US16/705,639 US201916705639A US2020199311A1 US 20200199311 A1 US20200199311 A1 US 20200199311A1 US 201916705639 A US201916705639 A US 201916705639A US 2020199311 A1 US2020199311 A1 US 2020199311A1
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United States
Prior art keywords
particles
elastomeric
film
article
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US16/705,639
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English (en)
Inventor
Khon Pu Foo
Chin Keong Lim
Nurshamila Binti Shaari Balakrishna
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Skinprotect Corp Sdn Bhd
Original Assignee
Skinprotect Corp Sdn Bhd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from AU2018904670A external-priority patent/AU2018904670A0/en
Application filed by Skinprotect Corp Sdn Bhd filed Critical Skinprotect Corp Sdn Bhd
Assigned to SKINPROTECT CORPORATION SDN BHD reassignment SKINPROTECT CORPORATION SDN BHD ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BALAKRISHNA, Nurshamila Binti Shaari, FOO, KHON PU, LIM, Chin Keong
Publication of US20200199311A1 publication Critical patent/US20200199311A1/en
Priority to US16/919,889 priority Critical patent/US20200385537A1/en
Abandoned legal-status Critical Current

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Definitions

  • any modifications that would need to be made to the formulation or manufacturing method would need to be viable from a variety of perspectives, including final film properties, colour, fluidity of mixtures, strength of film, softness of film, flexibility of film (as indicated by elongation), and so forth. It was not readily predictable or expected that the desired objective of multi-detectability would be achievable, while maintaining acceptable film properties, particularly for a glove product.
  • the elastomeric film-forming composition further comprises a viscosity modifier.
  • a viscosity modifier in ensuring that the particles incorporated into the composition remain well dispersed throughout the composition, and are picked-up into the elastomeric film layer (particularly during dip-production) rather than settling out of solution or pooling in an uneven manner within the film layer prior to curing.
  • the corrosion inhibitor creates a protective particle coating that prevents or reduces contact between the magnetic particle core and water and/or oxygen that comes into contact with the particles in the film layer during production or in use.
  • 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 by a corrosion inhibitor, and/or a corrosion inhibitor is dispersed throughout said film layer containing the magnetic particles.
  • film thickness and weight apply for articles containing corrosion inhibitor-coated magnetic particles, or containing magnetic particles with a non-coating inclusion of a corrosion inhibitor.
  • film thickness and weight also apply for articles containing one of the particle types only (e.g. magnetic particles, which may be coated or uncoated), together with a pseudoplastic viscosity modifier.
  • corrosion of particular types of particles can be caused by either (1) oxidation (i.e. general corrosion), (2) chemical exposure to corrosive agents (e.g. by chlorine or sulphur), or (3) by exposure to acid or basic substances in end-use applications (e.g. foodstuffs that are acidic or basic that come into contact with the articles containing the particles—such as gloves).
  • Corrosion of types (1) and (2) are particularly relevant to the presence of the corrodible particles that make up particles (a(i)), (a(ii)) and/or (b) in the elastomeric film-forming composition used to make the articles.
  • compositions that are used for dip-forming gloves are based on aqueous suspensions of an elastomeric polymer (“latex”) contain substances including water, chlorine and/or sulphur that can cause corrosion of the particles, and discolouration as a consequence.
  • latex an elastomeric polymer
  • a subclass of corrosion inhibitors are the hydrophobic corrosion inhibitors. Such materials provide corrosion inhibition through creating a hydrophobic coating around the particles that repels water, to protect the core particles from corrosion caused by water. Examples include hydrophobic polymers, waxes and silicones.
  • Technique (iii) outlined above involves chemically reacting the surface of the particle with a suitable reagent, such as an acid that forms the desired conversion coating when reacted with the metal. This is normally done in the process of conversion coating, where a layer of corrosion inhibitor is chemically formed or deposited on the surface of the metal particle.
  • suitable corrosion inhibitor coating materials that may be formed by a process of conversion coating are oxides such as iron oxides, chromates, phosphates, aluminate, oxalate, zirconate, and molybdates.
  • the particle core typically comprises a metal or combination of metals in the metallic state.
  • conversion coating techniques are only suited to some classes of particles.
  • the corrosion inhibitor coating, or layer allows metallic particles to be incorporated into water-based systems (e.g. water-based elastomeric film-forming compositions) without being susceptible to oxidation.
  • water-based systems e.g. water-based elastomeric film-forming compositions
  • This enables the production of metal detectable gloves containing pure metal particles or their alloys with better magnetization strength or high atomic weight elements, without concern for corrosion of those metals/alloys, thus producing enhanced detectability.
  • This in turn enables the amount of particles (by wt % or phr) to be reduced, while still achieving sufficient detectability levels in small volumes of the elastomeric film.
  • the relative amount of corrosion inhibitor coating to particle core may be between 5 and 50% by weight.
  • the amount of corrosion inhibitor coating may optionally be within the range of 10-35% by weight, or about 10-15% by weight, based on the total particle weight.
  • the amount is more readily determined for coating techniques that involve the addition of a coating layer to the particles. In the case of conversion coatings, or the formation of the coating layer in situ, it may be more difficult to determine the relative amounts. Nevertheless, for such coating techniques, the coating is sufficient to surround the cores and to produce an effective corrosion resistant coating around the particles.
  • the elastomeric film-forming composition comprises an elastomer-forming polymer (or polymer for short), in suspension or emulsion form.
  • the polymer may be natural rubber or a synthetic polymer.
  • the polymer is one that can be cross-linked to produce an elastomeric film.
  • the polymer may be a single polymer or a combination (blend) of two or more polymers.
  • the or each polymer may be a homopolymer or a copolymer, a grafted or modified polymer, or a blend thereof.
  • thermoplastic elastomers examples 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 compound; copolyester elastomers; metallocene-catalyzed polyolefin elastomers such as very low molecular weight, linear low density polyethylenes (VLMW-LLDPE); and reactor-made thermoplastic polyolefin elastomers.
  • the articles are generally PVC-free articles.
  • ASE thickeners are a known class of materials, based on a dispersion of acid-functional acrylic polymers in water.
  • One example is Rheovis AS1125, but many others are available. (Hydrophobically-modified ASE thickeners, however, are preferably avoided.)
  • the pseudoplastic properties can be measured by preparing a formulation (dip formulation containing latex, cross-linkers, particles, etc.) containing the selected viscosity modifier, measuring the viscosity (Brookfield viscometer, spindle no. 3, 30 rpm) after 24 hours, and comparing this to the viscosity measured at 60 rpm after 24 hours. If the viscosity is less at 60 rpm, then this indicates pseudoplastic properties.
  • Nitrile latex with sodium aluminate, sulphur and ZDBC.
  • Formulation H Nitrile compound with MDP 4 Material Amount (phr) Nitrile latex 100 Potassium hydroxide 1.7 Ionic crosslinking agent (sodium 0.15 aluminate) Covalent crosslinking agent 0.2 (Sulphur) Accelerator (ZDBC) 0.2 Antioxidant 0.3 MDP 4 ⁇ Magnetite + bismuth 30 oxide Opacifier 3.0 Viscosity modifier (pseudoplastic 6.0 acrylic based emulsion) pH adjuster 0.6 Viscosity at 25° C., spindle 3, 30 rpm: 476 cps
  • the formulation was also produced with the same components as listed above, but with lower amounts of viscosity modifier and pH adjuster (4.5 and 0.5 phr, respectively).
  • Table 29 shows overall migration values which indicate that all gloves tested were below the overall migration limit of 10 mg/dm 2 .
  • detectable fillers to the glove, the migration of soluble or insoluble materials was lessened. It is postulated that, not only did the detectable particles not demonstrate any particular tendency to migrate out of the glove product, they also appeared to act as a barrier which restricted the tendency for other soluble or insoluble materials in the glove to migrate outwards. For the glove having the same thickness as the control glove, the migration level was lower, which is a positive additional effect of including particles (a) and (b) in the gloves.
  • Gloves produced in accordance with the formulations of the examples have radiation attenuation properties. This provides additional functionality to the gloves.
  • Table 33 shows the attenuation ratio at different x-ray intensities, 70 kV and 100 kV, whereby a higher radiation intensity would normally show a lower attenuation ratio value.
  • the multi-detectable glove type XIII had a larger tendency to attenuate radiation compared to control glove, despite having a similar thickness.
  • the presence of particles (b) allows for a higher degree of radiation attenuation, whereas the presence of particles (a(i)) allows metal detection.
  • the films of the present application demonstrated detectability for volumes as low as 5.0 mm mm 3 and 1.0 mm 3 .
  • the amount of metallic tin (by volume) in a 50 mm 3 film, based on 67% by weight loading, is estimated to be less than the content (by volume) of tungsten in film type B which had a size of 400 mm 3 . Since tungsten is known to be more conductive than metallic tin, it is deduced that a 50 mm 3 glove piece containing 67% metallic tin by weight is also not detectable (similar to the tungsten example that was subjected to the test outlined above).
  • Formulation L was prepared as follows:
  • An elastomeric article comprising an elastomeric film containing one or more film layers, and at least two types of particles including:
  • An elastomeric film-forming composition comprising:
  • elastomeric article of any one items 86 to 95 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 elastomers and combinations or co-polymers thereof.

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US20210401096A1 (en) * 2020-06-26 2021-12-30 Top Glove International Sdn. Bhd. Latex formulation and x-ray detectable glove prepared thereof
EP3964094A1 (en) * 2020-09-02 2022-03-09 Top Glove International Sdn. Bhd. Glove
CN114654836A (zh) * 2022-03-30 2022-06-24 安丹达工业技术(上海)有限公司 一种防护设备的可探测层、该防护设备及其制造方法
US11839247B2 (en) * 2019-09-20 2023-12-12 Detectamet Limited Gloves and the manufacture thereof
US12049584B2 (en) * 2019-03-18 2024-07-30 Sabine Zureikat Composition and method for producing the sensory stimulant
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US12049584B2 (en) * 2019-03-18 2024-07-30 Sabine Zureikat Composition and method for producing the sensory stimulant
US11839247B2 (en) * 2019-09-20 2023-12-12 Detectamet Limited Gloves and the manufacture thereof
US20210189104A1 (en) * 2019-12-20 2021-06-24 Church & Dwight Co., Inc. Polymer compositions and products formed therewith
US12415908B2 (en) 2019-12-20 2025-09-16 Church & Dwight Co., Inc. Polymer compositions and products formed therewith
US12509572B2 (en) 2019-12-20 2025-12-30 Church & Dwight Co., Inc. Polymer compositions and products formed therewith
US12528936B2 (en) 2019-12-20 2026-01-20 Church & Dwight Co., Inc. Polymer compositions and products formed therewith
US20210401096A1 (en) * 2020-06-26 2021-12-30 Top Glove International Sdn. Bhd. Latex formulation and x-ray detectable glove prepared thereof
US11952478B2 (en) * 2020-06-26 2024-04-09 Top Glove International Sdn. Bhd. Latex formulation and X-ray detectable glove prepared thereof
EP3964094A1 (en) * 2020-09-02 2022-03-09 Top Glove International Sdn. Bhd. Glove
US11944140B2 (en) 2020-09-02 2024-04-02 Top Glove International Sdn. Bhd. Glove
CN114654836A (zh) * 2022-03-30 2022-06-24 安丹达工业技术(上海)有限公司 一种防护设备的可探测层、该防护设备及其制造方法

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