JP2018538462A - gloves - Google Patents

Abstract

  Disclosed is a magnetically detectable glove that includes at least one layer of a polymeric material that includes coated iron oxide nanoparticles. The coated iron oxide nanoparticles are present in an amount of 5-25 per 100 parts of the material, the coated iron oxide nanoparticles are ≧ 90% magnetite and have a particle size size of 6-25 nm. And has a magnetization strength (Ms) of 62 to 75 emu / g.

Description

  The present disclosure relates to a magnetite modified glove that can be detected with a vibrating sample magnetometer (VSM) or a metal detector (eg, Nissin MS3137).

  In this specification, a list or discussion of a document that has been disclosed previously is not necessarily to be construed as an admission that the document is part of the state of the art or common general knowledge.

  Contamination of any type of material (eg rubber) found in the final food product can be a nightmare in public relations for brands and food manufacturers, regardless of their size (http: //en-gb.eriez .com / resources / content / en-b / documents / pdfs / Polymag_Additives_White_Paper.pdf Collins, 2012 Eriez Orange University). For example, contamination of just a small piece of glove can lead to a recall of the entire manufacturing process and a potential lawsuit. For those who follow the process of recalling food, “contamination of gloves” is a common phrase. From cakes to tuna and dog food, the discovery of glove contamination is a familiar and troublesome event for both customers and producers. Ensuring effective means to prevent contamination of food products is a major concern for food manufacturers. Contamination accidents not only cause production line outages and suffer enormous damage, but also reclaim consumer confidence and require tremendous time and money to reconstruct the damaged brand image. Finding a solution to the glove contamination problem has long been a challenge, as ordinary gloves cannot be detected by metal detectors.

  One solution to the above problem is iron oxide (US Pat. No. 5,922,482; International Patent Application No. 2002/071876) or steel, lead, silver (US Pat. No. 6,734,245). Use magnetically detectable gloves that can be made from a variety of magnetic inorganic materials such as US Patent Application Publication No. 2011/0231983) and chromium (US Pat. No. 7,122,593). Most of these gloves are made by incorporating a proportion of inorganic material that is present throughout the product. The size and concentration of the magnetic material is intended to distribute a uniform amount of the material throughout the glove, which ensures that all parts of the glove are potentially detectable by the detector. Trying to.

  However, the above-mentioned glove challenges include the fact that the size of the glove piece may not have to be relatively large to ensure that the detection is detected. This may be due to the relatively poor magnetic properties (eg, low saturation magnetization and / or high coercivity) in the glove in question, or dispersion uniformity issues. Thus, there remains a need to provide improved magnetic gloves that provide higher sensitivity in detection while remaining worn by the end user.

  The above problem is a new form of coated iron oxide nanoparticles that have better magnetic properties and remain uniformly dispersed over a long period of time in a liquid (eg, water or polymer medium). Solved by use.

Accordingly, in a first aspect of the present invention there is provided a magnetically detectable glove comprising at least one layer of a polymeric material comprising coated iron oxide nanoparticles,
Coated iron oxide nanoparticles are present in an amount of 5-25 per 100 parts of the material (e.g., 8-20 per 100 parts of the material),
The coated iron oxide nanoparticles are
(I) ≧ 90% (eg, ≧ 95%) magnetite,
(Ii) having a particle size of 6-25 nm (e.g., 8-23 nm) measured using a transmission electron microscope;
(Iii) 62-75 emu / g (for example, 65-68 emu / g) of magnetization intensity (Ms),
Optionally, the glove has a magnetization saturation of 1 emu / g to 12 emu / g (eg, 1.05 emu / g to 6.0 emu / g, 1.10 emu / g to 4.0 emu / g, etc.) and / or 8 to 15 kA / m (for example, 8.93 to 14.33 kA / m).

In an alternative or additional second aspect of the present invention, there is provided a magnetically detectable glove comprising at least one layer of polymeric material comprising coated iron oxide nanoparticles,
Coated iron oxide nanoparticles are present in an amount of 5-25 per 100 parts of the material (e.g., 8-20 per 100 parts of the material),
Magnetization saturation of the glove of 1 emu / g to 12 emu / g (eg, 1.05 emu / g to 6.0 emu / g, 1.10 emu / g to 4.0 emu / g, etc.) and / or 8 to 15 kA / m ( For example, iron oxide nanoparticles with a coercivity of 8.93 to 14.33 kA / m) and optionally coated are:
(I) ≧ 90% (or 90% or more, ≧ 90%) (eg, ≧ 95%) magnetite,
(Ii) having a particle size of 6-25 nm (e.g., 8-23 nm) measured using a transmission electron microscope;
(Iii) It has a magnetization intensity (Ms) of 62 to 75 emu / g (for example, 65 to 68 emu / g).

  In certain embodiments of the present invention, the polymeric material may be any suitable polymeric material that can be used to make a glove. More particularly, the polymeric material may be selected from one or more of the group consisting of synthetic rubber, natural rubber, high density polyethylene, low density polyethylene, polyamide and PVC. For example, the polymeric material may be styrene butadiene rubber, polychloroprene rubber, synthetic polyisoprene rubber, polyurethane rubber, or more specifically nitrile rubber.

  In a further embodiment of the invention, the coated iron oxide nanoparticles may be distributed throughout the material layer so that the entire glove can be detected with a magnetic sensor. For example, at least a 3 mm × 3 mm piece of glove having a minimum thickness of 0.05 mm to 0.15 mm can be detected (eg, using Nisshin MS3137).

  The coated iron oxide nanoparticles are coated with a coating agent. The coating agent is composed of oleic acid, hexadecanoic acid, tetradecanoic acid, dodecanoic acid, undecanoic acid, decanoic acid, stearic acid, hexanoic acid, nonaic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, mercaptosilane and aminosilane. It may be selected from a group. Certain embodiments that may be referred to herein may relate to iron oxide nanoparticles coated with oleic acid. In certain embodiments, the coating may form a bilayer coating (or coating, coating) on the surface of the iron oxide nanoparticles. In alternative embodiments, the coating may be a single layer coating or a multilayer coating.

  In still further embodiments of the present invention, the coated iron oxide nanoparticles may have a weight / weight ratio greater than 0.2: 1 (eg, 2.5: 1 to 2: 1, 3: 1 to 1: 1) and the like, and may be coated with a coating agent bonded to the surface of the iron oxide nanoparticles.

In a still further embodiment of the invention, the coated iron oxide nanoparticles are
(I) a polydispersity index of 0.13 to 0.25 (eg, 0.14 to 0.20);
(Ii) 0.80 to 1.07 emu / g (eg, 0.85 to 1.00 emu / g) remanence,
(Iii) a coercivity (Hc) of 6.47 to 8.57 kA / m (eg, 6.95 to 7.75 kA / m),
(Iv) a zeta potential of −45 to −55 mV (eg, −50 to −51 mV),
(V) Magnetic strength that decreases by 1% to 6% (eg, 2% to 5.5%, 5.2%, etc.) when subjected to oxidation,
(Vi) It may have one or more of water stability or water / latex medium stability from 20 days to 100 days (eg, 30 days to 90 days, 30 days to 90 days, etc.).

In a still further embodiment of the invention, the glove is 1 emu / g to 12 emu / g (e.g., 1.05 emu / g to 6.0 emu / g, 1.10 emu) measured using a 20 mm ² portion of the glove. / G to 4.0 emu / g, etc.). The coercivity of the glove may be a coercivity of 8-15 kA / m (e.g., 8.93-14.33 kA / m) measured with a VSM using a 20 mm ² portion of the glove. It will also be appreciated that smaller pieces of the glove can provide similar properties (eg, examples where the coercivity of the glove is measured using 3 mm ² portions of various regions of the glove). See).

  In certain embodiments of the invention, the glove may have soft magnetic properties due to the very low coercivity and remanence values of the coated iron oxide nanoparticles.

In a still further embodiment of the invention, the glove is
(A) a thickness of 0.05 to 0.11 mm (eg 0.07 to 0.10 mm) measured according to ASTM D3767, and / or (b) a tensile strength of 23.3 to 29.7 MPa according to ASTM D412; And / or (c) may have an elongation of 558 to 660% measured according to ASTM D412.

  In a still further embodiment of the invention, the glove may further comprise one or more additional layers of polymeric material that do not comprise coated iron oxide nanoparticles, and optionally the glove is coated with iron oxide nanoparticles. It further includes at least two additional layers of polymeric material that do not include particles, the layer sandwiching a layer of polymeric material that includes coated iron oxide nanoparticles. The one or more additional layers of polymeric material may be the same or different from the polymeric material used to incorporate the coated iron oxide nanoparticles and may be selected from similar materials as defined above. That will be recognized.

  In a still further embodiment, the glove may meet the criteria set by ASTM D6319 and EN 455.

  In a second aspect of the invention, there is provided a method of manufacturing a glove according to any one of the above claims, the process of which is 5-25 phr (e.g. 8-20 phr) before forming the glove. Incorporating the coated iron oxide nanoparticles into a polymeric material, wherein the coated iron oxide nanoparticles exhibit one or more of the properties described above.

  In embodiments of this aspect, the polymeric material can be any suitable polymeric material that can be used to make a glove. More particularly, the polymeric material may be selected from one or more of the group consisting of synthetic rubber, natural rubber, high density polyethylene, low density polyethylene, polyamide and PVC. For example, the polymeric material may be styrene butadiene rubber, polychloroprene rubber, synthetic polyisoprene rubber, polyurethane rubber, or more specifically nitrile rubber.

  In still further embodiments of the present invention, the process may further comprise obtaining a glove formed from the process described above and adding one or more additional layers of polymeric material. The one or more additional layers of polymeric material may be the same as or different from the layer of polymeric material incorporating the coated iron oxide nanoparticles.

  The features of the present invention will be more readily understood and appreciated from the following detailed description when taken in conjunction with the accompanying drawings of embodiments of the invention.

FIG. 1 is a graph showing tensile strength (TS), elongation (% EB) and elastic modulus (M300) for various phrs of nanoMAG slurry content in magnetically detectable NBR gloves. 2 (a) shows a control NBR glove, FIG. 2 (b) shows a magnetically detectable NBR glove according to the present invention, and FIG. 2 (c) shows a test position in the magnetically detectable NBR glove. 3 shows NBR at various iron oxide loadings for (a) NBR-nanoMAG (composite material according to the invention) thin film, and (b) NBR-nanoMAG gloves made from the same material. 3 shows magnetization saturation of a composite material FIG. 4 shows the magnetization saturation of NBR gloves with various loadings of nanoMAG (a) 5; (b) 8; (c) 10; (d) 13; and (e) 15 phr.

  By incorporating nano-MAG (coated iron oxide nanoparticles) during manufacturing, broken pieces or fragments of gloves mixed into food products can be detected with a metal detector inspection system, Allows manufacturers to prevent contaminated products from reaching the market. The present invention allows the food processing machine to detect and detect undesirable elements before the final product reaches the consumer in order to reduce the risk of unwanted media attention and legal issues while maintaining product safety and quality. We are investigating how detectable nanoMAG can help to fail.

Accordingly, there is provided a magnetically detectable glove comprising at least one layer of polymeric material comprising coated iron oxide nanoparticles,
Coated iron oxide nanoparticles are present in an amount of 5-25 per 100 parts of the material (e.g., 8-20 per 100 parts of the material),
The coated iron oxide nanoparticles are
(I) ≧ 90% (eg, ≧ 95%) magnetite,
(Ii) having a particle size of 6-25 nm (e.g., 8-23 nm) measured using a transmission electron microscope;
(Iii) It has a magnetization intensity (Ms) of 62 to 75 emu / g (for example, 65 to 68 emu / g).

In embodiments of this aspect, the glove is optionally measured with a 20 mm ² portion of the glove from 1 emu / g to 12 emu / g (eg, 1.05 emu / g to 6.0 emu / g, 1.10 emu / g). May have magnetization saturation of .about.4.0 emu / g). The coercivity of the glove may be a coercivity of 8-15 kA / m (e.g., 8.93-14.33 kA / m) measured with a VSM, optionally using a 20 mm ² portion of the glove.

In an alternative aspect of the present invention, there is provided a magnetically detectable glove comprising at least one layer of polymeric material comprising coated iron oxide nanoparticles,
Coated iron oxide nanoparticles are present in an amount of 5-25 per 100 parts of the material (e.g., 8-20 per 100 parts of the material),
Magnetization saturation of the glove of 1 emu / g to 12 emu / g (eg, 1.05 emu / g to 6.0 emu / g, 1.10 emu / g to 4.0 emu / g, etc.) and / or 8 to 15 kA / m ( For example, it has a coercive force of 8.93 to 14.33 kA / m). In an embodiment of this aspect, the coated iron oxide nanoparticles are
(I) ≧ 90% (eg, ≧ 95%) magnetite,
(Ii) may have a particle size of 6-25 nm (eg, 8-23 nm) measured using a transmission electron microscope;
(Iii) It may have a magnetization intensity (Ms) of 62 to 75 emu / g (for example, 65 to 68 emu / g).

Magnetization saturation may be measured using a magnetosensitive sensor (eg, a metal detector, Nisshin M3137, etc.) or a vibrating sample magnetometer (VSM), optionally using a 20 mm ² portion of the glove. The coercivity may be measured using a VSM and optionally using a 20 mm ² portion of the glove.

  The crystallinity (or crystallization ratio, percentage crystallization, percent crystallininty) of the iron oxide nanoparticles described herein may be measured by any suitable method. For example, crystallinity may be measured using Mossbauer spectroscopy.

The coated iron oxide nanoparticles can be obtained by coating the raw iron oxide nanoparticles with a coating agent. These raw iron oxide nanoparticles have ≧ 90% (eg, ≧ 95%) magnetite (Fe ₃ O ₄ ) and the following properties:
When measured using a transmission electron microscope, the particle size is 7 to 27 nm (for example, 12 to 25 nm, 20 to 23 nm, etc.), and 60 to 80 emu / g (for example, 65 to 75 emu / g, 67 to 70 emu / g)), etc. (Ms)
including.

In addition, the raw material iron oxide nanoparticles,
85-99% crystallinity (eg, ≧ 90% or ≧ 95% magnetite),
A substantially spherical shape,
A polydispersity index of 0.15 to 0.25 (eg, 0.16 to 0.25, 0.17 to 0.20, etc.),
Remanence of 0.19 to 1.84 emu / g (eg, 0.25 to 1.50, 0.50 to 1.00 emu / g, etc.),
A coercivity (Hc) of 3.29 to 14.71 kA / m (eg, 4.20 to 11.00 kA / m, eg, 5.00 to 8.50 kA / m),
It may have a zeta potential of −33 to −49 mV (eg, −45 to −48 mV, −46.7 mV, etc.).

  Details of a method for obtaining raw iron oxide nanoparticles having these characteristics are shown below.

  The polymeric material may be any suitable polymeric material that can be used to make a glove. More particularly, the polymeric material may be selected from one or more of the group consisting of synthetic rubber, natural rubber, high density polyethylene, low density polyethylene, polyamide and PVC. For example, the polymeric material may be styrene butadiene rubber, polychloroprene rubber, synthetic polyisoprene rubber, polyurethane rubber or nitrile rubber. In certain embodiments of the invention described herein, the polymeric material may be nitrile rubber.

  The coated iron oxide nanoparticles may be distributed throughout the material layer so that the entire glove can be detected with a magnetic sensor. For example, at least a 3 mm x 3 mm piece of glove having a minimum thickness of 0.05 mm to 0.15 mm may be detectable using a suitable metal detector. For example, the Nisshin MS3137.

  The coated iron oxide nanoparticles are coated with a coating agent. Specific coatings that may be mentioned herein are oleic acid, hexadecanoic acid, tetradecanoic acid, dodecanoic acid, undecanoic acid, decanoic acid, stearic acid, hexanoic acid, nonanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, A coating selected from the group consisting of mercaptosilane and aminosilane may be included. Particular examples that may be mentioned herein may relate to iron oxide nanoparticles coated with oleic acid.

  The coating may form a bilayer coating on the surface of the iron oxide nanoparticles. As used herein, “bilayer coating” means a first coating layer of a coating that is in contact with iron oxide nanoparticles and a second coating layer that is in contact with the first coating layer. . These separate layers may be held in place by non-covalent attractive forces (or non-covalent attractive forces). Accordingly, single layer coatings and multilayer coatings may be interpreted. In certain embodiments of the invention that may be referred to herein, the coating may be in the form of a two layer.

  The coated iron oxide nanoparticles have a weight / weight ratio greater than 0.2: 1 (eg, 2.5: 1 to 2: 1, 3: 1 to 1: 1, etc.) and the surface of the iron oxide nanoparticles. May be coated with a coating bonded to the.

The coated iron oxide nanoparticles have the following characteristics:
(I) a polydispersity index of 0.13 to 0.25 (eg, 0.14 to 0.20);
(Ii) 0.80 to 1.07 emu / g (eg, 0.85 to 1.00 emu / g) remanence,
(Iii) a coercivity (Hc) of 6.47 to 8.57 kA / m (eg, 6.95 to 7.75 kA / m),
(Iv) a zeta potential of −45 to −55 mV (eg, −50 to −51 mV),
(V) Magnetic strength that decreases by 1% to 6% (eg, 2% to 5.5%, 5.2%, etc.) when subjected to oxidation,
(Vi) It may have one or more of water stability or water / latex medium stability from 20 days to 100 days (eg, 30 days to 90 days, 30 days to 90 days, etc.).

The glove may have a magnetization saturation of 1 emu / g to 12 emu / g (eg, 1.05 emu / g to 6.0 emu / g, 1.10 emu / g to 4.0 emu / g, etc.). For example, it is measured using a 20 mm ² part of a glove. The coercivity of the glove may optionally be a coercivity of 8-15 kA / m (eg, 8.93-14.33 kA / m) measured with VSM using a 20 mm ² portion of the glove. It will be appreciated that other locations of the film (or film) provide similar results, at least for coercivity, as demonstrated by the example where 3 mm ² provides similar results.

  Without wishing to be bound by theory, the glove gains soft magnetic properties due to the very low coercivity and remanence values of the coated iron oxide nanoparticles used in the glove. Particularly good results obtained with gloves can be obtained.

Gloves
(A) a thickness of 0.05 to 0.11 mm (eg 0.07 to 0.10 mm) measured according to ASTM D3767, and / or (b) a tensile strength of 23.3 to 29.7 MPa according to ASTM D412; And / or (c) may have an elongation of 558 to 660% measured according to ASTM D412.

  That is, the glove may meet the criteria set by ASTM D6319 and EN 455.

  The glove may further include one or more additional layers of polymeric material that does not include coated iron oxide nanoparticles, and optionally the glove includes at least two of the polymeric material that does not include coated iron oxide nanoparticles. Additional layers are further included that sandwich a layer of polymeric material that includes coated iron oxide nanoparticles. It will be appreciated that the one or more additional layers of polymeric material may be the same or different from the polymeric material used to incorporate the coated iron oxide nanoparticles and may be selected from similar materials. It will be.

  The gloves described above may be manufactured and coated in a process that includes incorporating 5-25 phr (eg, 8-20 phr) of coated iron oxide nanoparticles into the polymer material prior to forming the glove. The iron oxide nanoparticles exhibit one or more of the properties described above.

  As described above, the polymeric material may be any polymeric material suitable for forming a glove. More particularly, the polymeric material may be selected from one or more of the group consisting of synthetic rubber, natural rubber, high density polyethylene, low density polyethylene, polyamide and PVC. For example, the polymeric material may be styrene butadiene rubber, polychloroprene rubber, synthetic polyisoprene rubber, polyurethane rubber or nitrile rubber. In certain embodiments of the invention described herein, the polymeric material may be nitrile rubber.

  It will be appreciated that the process may further comprise obtaining a glove formed from the process described above and adding one or more additional layers of polymeric material. The one or more additional layers of polymeric material may be the same as or different from the layer of polymeric material incorporating the coated iron oxide nanoparticles.

Gloves are made of nano-MAG (coated iron oxide nanoparticles:
(I) ≧ 90% (eg, ≧ 95%) magnetite,
(Ii) having a particle size of 6-25 nm (e.g., 8-23 nm) measured using a transmission electron microscope;
(Iii) 62-75 emu / g (for example, having a magnetization intensity (Ms) of 65-68 emu / g)
The invention will be described in more detail with respect to an embodiment that is a nitrile rubber (NBR) glove that incorporates.

  Although the following description and examples illustrate the preparation of magnetically detectable NBR gloves, it will be appreciated by those skilled in the art that the present invention can be applied to the manufacture of other magnetically sensitive gloves using other materials. It will be recognized that it will be understood.

  NBR glove latex and portions thereof can be prepared from a formulation that includes a nanoMAG wet cake (eg, nanoMAG incorporating a small amount of water). In certain embodiments, nanoMAG may be supplied dry and then water may be added to form a wet cake.

Iron oxide nanoparticles
(I) A mixture of FeCl ₂ (or a solvate thereof) and FeCl ₃ (or a solvate thereof) is supplied into a solvent, the mixture is reacted with NH ₄ OH, and iron oxide nanoparticles are contained. Forming a slurry;
(Ii) separating the iron oxide nanoparticles from the first slurry;
And (iii) washing uncoated iron oxide nanoparticles with a solvent to form a wet cake of uncoated iron oxide nanoparticles.

The separation step (ii) and the washing step (iii) include the following processes: (a) Applying magnetic force to the first slurry to precipitate (or collect, settle) the iron oxide nanoparticles and decant the solvent And (b) adding a solvent to form a second slurry, and then applying a magnetic force to the first slurry to precipitate the iron oxide nanoparticles and decanting the solvent to form a wet cake, and Optionally, (c) a step of repeating step (b) one or more times may be included.
In the above process,
(A) FeCl ₂ may be present as an FeCl ₂ .4H ₂ O solvate, FeCl ₃ may be present as an FeCl ₃ .6H ₂ O solvate, and / or (b) FeCl ₂ and / or FeCl ₂ (or its solvate) and FeCl ₃ (or its solvate) provided that the molar ratio is calculated based on the number of moles of solvate used when FeCl ₃ is present as a solvate. Product) may be present in a molar ratio of 0.5: 3 to 1: 1 (eg, 0.75: 2 to 1: 1.75, 1: 1.5, etc.).

In the above process, one or more of the following conditions may apply.
(A) In step (i), the solvent may be water;
(B) In step (i), NH ₄ OH may be a 12M aqueous solution and may be added to the mixture at a rate of 100 mL / min.
(C) In step (i), the mixture and the first slurry may be stirred at a speed of 100 rpm to 1000 rpm (for example, 200 rpm to 700 rpm, 500 rpm, etc.) using a mechanical stirrer.
(D) In step (i), the reaction temperature may be 50 to 70 ° C. (for example, 55 to 65 ° C., 60 ° C., etc.)
(E) In step (i), after adding the entire amount of NH ₄ OH, the first slurry may be stirred for 20 minutes to 120 minutes, such as 90 minutes,
(F) In step (i), after adding the entire amount of NH ₄ OH, the reaction may be continued until the first slurry has a pH of 9.5 or less.
For example, all of the above conditions may be applied.

  In addition, the iron oxide nanoparticles described above are further processed to provide coated iron oxide nanoparticles. These coated iron oxide nanoparticles further comprise a coating agent that coats the surface of the iron oxide nanoparticles. For example, the coating agent is selected from the group consisting of hexadecanoic acid, tetradecanoic acid, dodecanoic acid, undecanoic acid, decanoic acid, stearic acid, hexanoic acid, nonanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, mercaptosilane, aminosilane, and oleic acid. May be selected. Particular coatings that may be mentioned herein include oleic acid.

It may be necessary to increase the pH of the coated iron oxide nanoparticles by adding alkaline additives to ensure compatibility of the nanoparticles with the standards required for the formation of NBR latex gloves. Thus, for example, the coating process is carried out by adding various amounts of coating to semi-dry nanomagnetic iron oxide nanoparticles, stirring manually, and then adding 12M NH ₄ OH (as an alkaline agent). Good (amounts listed in Table 1). The resulting suspension is treated with ultrasound using an ultrasound generator (or sonicator) for 1 hour and is described herein as “NanoMAG”. It will be appreciated that the addition of an alkaline agent may be used to raise the pH of the iron oxide nanoparticle slurry to a pH range appropriate for incorporation in gloves. In addition, it will be appreciated that any suitable alkaline agent may be used in the process.

  The magnetically sensitive NBR gloves of the present invention can be made using standard latex dipping techniques. Magnetically sensitive NBR gloves are hand-shaped ceramic glove molds (or glove formers, glove formers, glove formers) immersed in a coagulant tank and then compounded with a mixture of chemicals. It can be produced by dipping in a liquid latex tank. The role of precoating the mold with a coagulant is to gel the latex to achieve the correct glove thickness, facilitating later removal of the magnetically detectable NBR gloves following subsequent processing. Can help. Prior to drying and curing in a heated oven, the wet latex gel on the mold is passed through a leaching tank to remove any remaining hydrophilic chemicals. Thereafter, the gloves are removed from the mold and packaged. The outer layer of the glove on the immersed mold will be the inner layer of the magnetically detectable NBR glove. The latex used to make the glove of the present invention can contain a vulcanizing agent that hardens the magnetically detectable NBR glove and produces a dry magnetically detectable NBR glove.

  Magnetically sensitive NBR gloves may be manufactured on a mass production line where a plurality of magnetically detectable NBR gloves are manufactured in a rapid, consistent manner. Such techniques transport and manipulate multiple glove molds in a series of chemical solutions and dispersions that make up the gloves. The mold is made of steel or more particularly ceramic, porcelain, aluminum or plastic. According to standard manufacturing processes, gloves may be manufactured directly on a mold that is transported from one step to the next.

  Magnetically sensitive NBR gloves may be composed of various materials with multiple immersions. For example, the mold may first be immersed in a coagulant having a premix of calcium nitrate, powder free mold (or powder free mold) mold release agent and wetting agent. The mold release agent facilitates later removal of the finished glove from the mold. In addition, the coagulant material will destabilize and gel the later liquid latex.

  After applying the mold release / coagulant dip, it is preferred to transport the mold to the next step in the production line where the laminate layer is applied to the mold. The laminate layer may include NBR latex. By changing the composition of the NBR latex material, the laminate layer may be changed to provide varying strength, comfort and flexibility.

  Preferably, after applying one or more laminate layers, the mold is passed through a heated oven, dried and cured to provide the final product. Thereafter, the gloves are removed either manually or by automated techniques. Numerous variations may be introduced in accordance with the above-described substantially automated mass production techniques to provide additional or various desirable properties of the laminate according to the present invention.

In an embodiment of the present invention, various NBR latex formulations were prepared to contain 5-25 parts by weight (phr) of nanoMAG concentration per 100 total NBR latex. The component units for the following formulations were based on the dry solids content of the latex set to 100 parts, with all other components set to parts per 100 rubber ("phr"). NanoMAG is added and mixed to form a latex, forming a substantially uniform dispersion of nanoMAG. Some settling can occur. However, by stirring / stirring during blending and mixing so that the nanoMAG is uniformly dispersed in the NBR latex layer of the porcelain-detectable NBR gloves, and continuously in the latex soak tank during soaking It is preferable to uniformly disperse nanoMAG in the NBR latex by stirring.
Examples of various formulations are shown in Table 2.

  The following examples illustrate the invention in more detail.

Protocol for Measuring Metal Detectability of Measurement Gloves Table 3 shows the settings of Nisshin's MS3137 machine.

Sample preparation:
1. The glove film to be measured is cut into 3 × 3 mm pieces and then laminated with a transparent polymer film having a thickness of 100 μm. Further, the foamed styrene block was cut into a 20 × 20 × 20 mm cube.
2. Laminated sample film and step 1 expanded styrene cubes are placed side by side and passed through the center of Nissin using the settings in Table 3.
3. To verify detection / non-detection, steps 1 and 2 were repeated 3 times for the same sample.
Note: If metal is detected in the sample, the conveyor will stop immediately.

Zeta Sizer Malvern's Zeta Sizer Nano ZS was selected to investigate the zeta potential, particle size distribution and polydispersity of IONP (iron oxide nanoparticles). This is a high performance bi-angle particle and molecular size analyzer with dynamic light scattering used for high detection of aggregation and measurement of small or diluted samples and very low or high concentration samples. is there. This technique measures the diffusion of particle movement based on Brownian motion and then converts it to size and size distribution using the Stokes-Einstein relationship. About 0.001 g of IONP was prepared and dispersed in 5 ml of DI water. Further, 0.2 ml of 3M ammonium hydroxide was added dropwise. The solution is about pH 10. The solution was sonicated for 1 hour to ensure that the IONP was well dispersed in deionized water. The Zetasizer instrument was turned on for 30 minutes to stabilize the laser. The dispersion solution is then placed in disposable polystyrene (DTS0012) and folded capillary cells (DTS1060) that measure hydrodynamic size (or hydrodynamic size) and zeta potential, respectively. Injected into. Then the required cell was inserted into the instrument and the temperature was stabilized. Finally, the slurry charge (or charge) and particle size distribution measurements were analyzed and the results collected.

High resolution transmission electron microscope (HRTEM)
HRTEM analysis was performed with a JEM-2100F instrument at an acceleration voltage of 200 kV. This has been a major support in the list of characterization techniques for material scientists who consider the ability to extract both image and diffraction information from a single sample. Furthermore, the material properties can be determined by the radiation produced by the beam electrons accelerated on the sample. This provides a high magnification of up to 1.6 times where very small and fine plaid spacing can be observed. Samples were prepared by dropping the dispersed IONP onto a 300 mesh copper grid prior to HRTEM characterization. The prepared sample was left overnight. The sample prepared on the copper grid was then placed in the HRTEM sample holder before being inserted into the HRTEM. IONP images were selected and taken at 50000, 100,000 and 500,000 magnifications. Size and checker spacing were measured with image-J. After measuring 100 IONP particles, the particle size distribution can be plotted and the fringe spacing was used to support the XRD information.

Vibration sample type magnetometer (VSM)
VSM was invented in 1956 by Simon Foner (MIT scientist) and is widely used to determine the magnetic properties of a wide variety of diamagnetic, paramagnetic, ferromagnetic and antiferromagnetic materials. ing. The magnetic properties of IONP were investigated using a vibrating sample magnetometer (Lakeshore-VSM7407). About 0.03 g of IONP was prepared in the sample holder and placed in the center of a pair of pickup coils between the poles of the electromagnet. The sample was attached to the sample rod of the transducer assembly and passed through the center of the drive coil. The transducer was driven by a power amplifier that was driven by an oscillator at a frequency of 71 Hz. The sample was vibrated along the z-axis perpendicular to the magnetic field (or magnetizing field) to induce a signal indicative of the magnetic properties themselves. The magnetization saturation (Ms), coercive force (Hc) and remanent magnetization (Mr) of IONP were confirmed by applying continuous hysteresis and magnetic field of 10,000 kA / m to -10000 kA / m and -10000 kA / m to 10000 kA / m.

Preparation 1
Preparation of iron oxide nanoparticles Completely dissolved aqueous solution of FeCl ₂ .4H ₂ O (28.16 g, 141.64 mmol, 100 mL) in 60 ° C. deionized (DI) water (680 mL) with vigorous stirring (500 rpm). In H ₂ O), and an aqueous solution of completely dissolved FeCl ₃ .6H ₂ O (57.42 g, 212.43 mmol, in 100 mL H ₂ O; FeCl ₂ .4H ₂ O / FeCl ₃ .6H ₂ O A molar ratio of 1: 1.5) was added continuously. Ammonium hydroxide (12M, 1000 mL) was then added to the above solution at a rate of 100 mL / min. The reaction mixture was stirred at 60 ° C. for an additional 90 minutes. The precipitate was separated from the reaction mixture using a magnet and washed with DI water (1000 mL). Excess water (about 950 mL) was removed and the nanomagnetic particles were kept semi-dry to prevent aggregation.

Preparation 2
Oleic acid (0.4 g) was added to the semi-dry nanomagnetic iron oxide nanoparticles and stirred manually, after which 12 M NH ₄ OH was added (amount listed in Table 4). The resulting suspension was treated with ultrasound for 1 hour using a sonic generator.

  The nanoMAG material used in the following examples was prepared using the process described above, but scaled up in proportion.

Example 1
The formulations in Table 5 below are embodiments of the present invention.

  Initially, the mixing tank was thoroughly cleaned with a brush and detergent to ensure there was no contamination during the compounding process. The NBR latex was filtered and transferred to a mixing tank. The latex was stirred for 30 minutes at a stirring speed of 50 rpm. Thereafter, the pH of the latex was adjusted to pH 9.6 to 9.7. Next, sodium dodecylbenzenesulfonate (SDBS) was slowly added to the latex and stirring was continued for 1 hour. Again, the pH of the compound latex was measured and adjusted to pH 9.6-9.7. The remaining chemicals excluding aqua wax (or water wax, Aquawax) and nanoMAG were slowly added to the latex compound and stirred for an additional hour. Thereafter, the stirring speed was lowered to 30 rpm and left overnight. At this stage, 5, 8, 10, 13 and 15 phr of coated nanoMAG and 12.04 g of aqua wax were slowly added to the formulated latex. The resulting mixture was stirred for 1 hour before use.

  485.68 g calcium nitrate (CN), 25 g perfluorocarboxylic acid (PFCA; powder free mold release agent) and 2 g non-ionic wetting agent (Teric 320) are added to 1487.32 g 60 ° C. water, The resulting mixture was poured into a coagulation tank to prepare a coagulant used to promote the coagulation of the latex on the mold surface. The formulated latex produced as described above was filtered and poured into a dip tank. Thoroughly clean the mold with soap and brush to prevent oily material or residual latex from leaving the mold (eg glove mold or template) that could cause defects in the final film / glove produced. Rinse with excess water.

  The mold was immersed in a coagulation tank to a predetermined level and then dried in an oven at 100 to 160 ° C. for 1 to 5 minutes. Thereafter, the dried mold was immersed in a latex immersion tank to a predetermined depth, and then dried at the same temperature for 5 minutes. After the latex-coated mold was removed from the oven, it was cooled to room temperature for 30 seconds before being dipped again into the latex dipping tank. The latex coated mold was cured at 125 ° C. (vulcanization temperature) for 20 minutes and then leached with 40 ° C. deionized (DI) water for 1 minute. The mold was then dried at 125 ° C. for 5 minutes. Finally, the mold was cooled at room temperature and the latex film / gloves were peeled from the mold. It will be appreciated by those skilled in the art that various parameters can be adjusted to ensure that the proper thickness of glove is obtained (eg, calcium nitrate concentration, total solids of the liquid latex, and latex Immersion profile).

  The thickness of the modified magnetically detectable NBR gloves was measured according to ASTM D3767 and mechanically tested according to ASTM D-412. FIG. 1 shows tensile strength (TS), elongation (% EB) and elastic modulus (M300).

  Figures 2 (a) and (b) show the results for magnetically detectable NBR gloves with (b) and without (a) nanoMAG incorporated. The magnetically detectable NBR glove shown in FIG. 2 (b) was found to have no nanoMAG aggregation.

  FIG. 2 (c) shows various test locations on a magnetically detectable NBR glove made according to the process described above. Tables 6-10 show the magnetic properties at various locations on the NBR glove that can be magnetically detected for 5, 8, 10, 13 and 15 phr nanoMAG, respectively.

  As shown in these tables, it appears that the fingertip location has a higher magnetic strength and the wrist location has a lower magnetic strength compared to other locations. This is because the film thickness at the fingertip region is usually thicker than the other regions, while the wrist region is usually thin, so that the amount of nanoMAG material is evenly distributed in the film. Indicates that

  The saturation magnetization of the magnetically detectable NBR film (a) and NBR gloves (b) for various loadings (0-15 phr) of nanoMAG slurry is shown in FIG. NBR-nanoMAG gloves were manufactured by the process described above, and NBR-nanoMAG thin films were manufactured using the process described above, using a square mold. It was observed that the magnetization saturation increased linearly as the iron oxide loading increased from 0 to 15 phr. However, the saturation magnetization of the NBR-nanoMAG thin film was higher than that of the NBR-nanoMAG glove, probably due to the thickness of the glove. The product exhibits very low coercivity and remanence, and the magnetic strength exhibits superparamagnetic properties. Accordingly, the product includes magnetite particles having soft magnetic properties.

  FIG. 4 shows the hysteresis curves of gloves / thin films with various phr loadings of nanoMag. As shown in FIG. 4, as the nano Mag loading increases, there is a significant increase in saturation magnetization observed in the glove / thin film ((a)-(e), D1 represents the batch of formulated latex used). means).

Example 3
A number of gloves with 5, 8, 10, 13 and 15 phr nanoMAG were made using the process and formulation described above, except that the gloves were provided using a single dipping in latex. Then, the above-mentioned magnetic detectability was tested about these gloves. The results are shown in Table 11 below.

  It will be appreciated that a nano MAG with a phr of 5 will not work at the stated thickness, but 5 phr will work if a thicker glove film is formed. In addition, it will be appreciated that thinner glove films will also work with increasing amounts of nanoMAG (phr).

Example 4
Using the process described above in Example 1, gloves containing 0-25 phr were prepared using the formulation detailed in Table 12.

  The physical properties of the gloves were tested before and after aging as detailed in Tables 13-15. The following values were determined with reference to each of the standard protocol tests described above.

  As used herein, “ASTM” refers to the American Society for Testing and Materials standards and associated protocols. “EN” means European standards and related protocols.

Claims (23)

A magnetically detectable glove comprising at least one layer of a polymeric material comprising coated iron oxide nanoparticles,
The coated iron oxide nanoparticles are present in an amount of 5-25 per 100 parts of the material (e.g., 8-20 per 100 parts of the material);
The coated iron oxide nanoparticles are
(I) ≧ 90% (eg, ≧ 95%) magnetite,
(Ii) having a particle size of 6-25 nm (e.g., 8-23 nm) measured using a transmission electron microscope;
(Iii) 62-75 emu / g (for example, 65-68 emu / g) of magnetization intensity (Ms),
Optionally, the glove has a magnetization saturation of 1 emu / g to 12 emu / g (eg, 1.05 emu / g to 6.0 emu / g, 1.10 emu / g to 4.0 emu / g, etc.) and / or 8 to 15 kA. / m (e.g., 8.93~14.33kA / m) has a coercive force of both optionally it is measured using a 20 mm ² portions of the glove, the glove. A magnetically detectable glove comprising at least one layer of a polymeric material comprising coated iron oxide nanoparticles,
The coated iron oxide nanoparticles are present in an amount of 5-25 per 100 parts of the material (e.g., 8-20 per 100 parts of the material);
The glove has a magnetization saturation of 1 emu / g to 12 emu / g (eg, 1.05 emu / g to 6.0 emu / g, 1.10 emu / g to 4.0 emu / g, etc.) and / or 8 to 15 kA / m. (e.g., 8.93~14.33kA / m) has a coercive force of both optionally is measured using a 20 mm ² portions of the glove,
The coated iron oxide nanoparticles are
(I) ≧ 90% (eg, ≧ 95%) magnetite,
(Ii) having a particle size of 6-25 nm (e.g., 8-23 nm) measured using a transmission electron microscope;
(Iii) A glove having a magnetization strength (Ms) of 62 to 75 emu / g (for example, 65 to 68 emu / g).   The glove according to claim 1 or 2, wherein the polymer material is selected from one or more of the group consisting of synthetic rubber, natural rubber, high density polyethylene, low density polyethylene, polyamide and PVC.   The glove of claim 3, wherein the polymeric material is styrene butadiene rubber, polychloroprene rubber, synthetic polyisoprene rubber, polyurethane rubber, or more specifically nitrile rubber.   The glove according to any one of claims 1 to 4, wherein the coated iron oxide nanoparticles are distributed over the entire material layer so that the entire glove can be detected by a magnetic sensor. .   6. At least 3mm x 3mm piece of glove having a minimum thickness of 0.05mm to 0.15mm is detectable (e.g. using Nisshin MS3137). Gloves.   The coated iron oxide nanoparticles are oleic acid, hexadecanoic acid, tetradecanoic acid, dodecanoic acid, undecanoic acid, decanoic acid, stearic acid, hexanoic acid, nonanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, mercaptosilane and aminosilane The glove according to any one of claims 1 to 6, which is coated with a coating agent selected from the group consisting of:   The glove according to claim 7, wherein the coated iron oxide nanoparticles are coated with oleic acid.   The glove according to claim 7 or 8, wherein the coating forms a two-layer coating on the surface of the iron oxide nanoparticles.   The coated iron oxide nanoparticles are in a weight / weight ratio greater than 0.2: 1 (eg, 2.5: 1 to 2: 1, 3: 1 to 1: 1, etc.). The glove according to any one of claims 1 to 9, wherein the glove is coated with a coating agent bonded to the surface.   The glove according to any one of claims 1 to 10, wherein the iron oxide nanoparticles have a polydispersity index of 0.13 to 0.25 (for example, 0.14 to 0.20). The iron oxide nanoparticles are
0.80 to 1.07 emu / g (eg 0.85 to 1.00 emu / g) remanence and / or 6.47 to 8.57 G (eg 6.95 to 7.75 kA / m) Coercive force (Hc)
The glove according to any one of claims 1 to 11, which has The coated iron oxide nanoparticles are
(I) has a zeta potential of −45 to −55 mV (eg, −50 to −51 mV) and / or (ii) 1% to 6% (eg, 2% to 5. And / or (iii) water stability from 20 days to 100 days (eg, 30 days to 90 days, 30 days to 90 days, etc.) or 13. A glove according to any one of the preceding claims having water / latex medium stability.   14. A glove according to any one of the preceding claims, wherein the glove has soft magnetic properties due to the very low coercivity and remanence value of the coated iron oxide nanoparticles. The gloves are
(A) a thickness of 0.05 to 0.11 mm (eg 0.07 to 0.10 mm) measured according to ASTM D3767, and / or (b) a tensile strength of 23.3 to 29.7 MPa according to ASTM D412; And / or (c) A glove according to any one of the preceding claims having an elongation of 558 to 660% measured according to ASTM D412.   The glove of claim 15, wherein the glove further comprises one or more additional layers of polymeric material that do not include coated iron oxide nanoparticles.   The one or more additional layers of polymeric material are at least two additional layers of polymeric material that do not include coated iron oxide nanoparticles, the layers including the coated iron oxide nanoparticles The glove of claim 16, sandwiching the layer of material.   The glove according to any one of claims 1 to 17, wherein the glove satisfies a standard set by ASTM D6319 and EN455. 19. The method for manufacturing a glove according to any one of claims 1 to 18, wherein the process comprises 5 to 25 phr (e.g. 8 to 20 phr) of coated iron oxide nano before forming the glove. Including incorporating particles into the polymeric material;
The coated iron oxide nanoparticles are
(I) ≧ 90% (eg, ≧ 95%) magnetite,
(Ii) having a particle size of 6-25 nm (e.g., 8-23 nm) measured using a transmission electron microscope;
(Iii) A method for producing a glove having a magnetization strength (Ms) of 62 to 75 emu / g (for example, 65 to 68 emu / g).   20. The method for manufacturing a glove according to claim 19, wherein the polymer material is selected from one or more of the group consisting of synthetic rubber, natural rubber, high density polyethylene, low density polyethylene, polyamide and PVC.   21. The method for manufacturing a glove according to claim 20, wherein the polymer material is styrene butadiene rubber, polychloroprene rubber, synthetic polyisoprene rubber, polyurethane rubber, or more specifically, nitrile rubber. The process further comprises adding one or more additional layers of polymeric material to the polymeric material incorporating the coated iron oxide nanoparticles;
22. Optionally, the one or more additional layers of polymer material may be the same as or different from the layer of polymer material incorporating the coated iron oxide nanoparticles. Manufacturing method of gloves.   The one or more additional layers of polymeric material are at least two additional layers of polymeric material that do not include coated iron oxide nanoparticles, the layers including the coated iron oxide nanoparticles The manufacturing method of the glove of any one of Claims 19-22 which has pinched | interposed the said layer of material.

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