JP7018888B2 - gloves - Google Patents

Description

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

In the present specification, the apparently previously published list or discussion of literature should not necessarily be taken as an admission that the literature is part of the latest technology or common sense of technology.

Contamination of any type of material (eg rubber) found in the final food product, regardless of its size, can be a nightmare in public relations for brands and food manufacturers (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 even the smallest pieces of gloves can lead to recalls and potential proceedings of the entire manufacturing process. For those who follow the process of food recall, "glove contamination" is a phrase that is too common. From cakes to tuna to dog food, the discovery of glove contamination is a familiar and annoying event for both customers and producers. Ensuring effective means of preventing contamination of food products is a major concern for food manufacturers. Contamination accidents not only require the shutdown of production lines and cause enormous damage, but also require enormous time and money to regain consumer confidence and rebuild a 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 problems 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 Chrome (US Pat. No. 7,122,593). Most of these gloves are made by incorporating a percentage of the inorganic material 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, ensuring that all parts of the glove are potentially detectable by the detector. Trying to.

However, the glove task described above includes the fact that the size of the glove fragment may not necessarily need to be relatively large to ensure that detection is detected. This may be due to the relatively poor magnetic properties of the glove in question (eg, low saturation magnetization and / or high coercive force), or the problem of dispersion uniformity. Therefore, there is still a need to provide improved magnetic gloves that provide higher sensitivity in detection while remaining wearable by the end user.

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

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

In an alternative or additional second aspect of the invention, a magnetically detectable glove comprising at least one layer of a polymeric material containing coated iron oxide nanoparticles is provided.
Coated iron oxide nanoparticles are present in an amount of 5-25 per 100 parts of the material (eg, 8-20 per 100 parts of the material).
Gloves 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.) and / or 8 to 15 kA / m (. For example, iron oxide nanoparticles having a coercive force of 8.93 to 14.33 kA / m) and optionally coated can be obtained.
(I) ≧ 90% (or 90% or more, ≧ 90%) (for example, ≧ 95%) magnetite.
(Ii) It has a particle size of 6 to 25 nm (eg, 8 to 23 nm) measured using a transmission electron microscope and has a particle size.
(Iii) has a magnetization strength (Ms) of 62 to 75 emu / g (for example, 65 to 68 emu / g).

In certain embodiments of the invention, the polymeric material may be any suitable polymeric material that can be used to make gloves. More specifically, the polymer material may be selected from one or more of the groups consisting of synthetic rubber, natural rubber, high density polyethylene, low density polyethylene, polyamide and PVC. For example, the polymer 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 magnetic sensor can detect the entire glove. For example, a fragment of at least 3 mm × 3 mm of a glove with a minimum thinness of 0.05 mm to 0.15 mm can be detected (eg, using Nissin's MS3137).

The coated iron oxide nanoparticles are coated with a coating agent. The coating agent consists of oleic acid, hexadecanoic acid, tetradecanoic acid, dodecanoic acid, undecanoic acid, decanoic acid, stearic acid, hexanic acid, nonaic acid, tridecanoic acid, pentadecaneic acid, heptadecanoic acid, mercaptosilane and aminosilane. It may be selected from the group. Certain embodiments that may be mentioned herein may relate to iron oxide nanoparticles coated with oleic acid. In certain embodiments, the coating may form a two-layer coating (or coating, coating, coating) on the surface of the iron oxide nanoparticles. In an alternative embodiment, the coating may be a single layer coating or a multi-layer coating.

In a further embodiment of the invention, 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). It may be coated with a coating agent bonded to the surface of iron oxide nanoparticles in 1 etc.).

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

In a further embodiment of the invention, the glove is 1 emu / g to 12 emu / g measured using 20 mm ² portions of the glove (eg, 1.05 emu / g to 6.0 emu / g, 1.10 emu). It may have a magnetization saturation of (/ g to 4.0 emu / g, etc.). The coercive force of the glove may be a coercive force of 8 to 15 kA / m (for example, 8.93 to 14.33 kA / m) measured by VSM using 20 mm ² portions of the glove. It will also be appreciated that smaller pieces of the glove may provide similar properties (eg, examples in which the coercive force of the glove is measured using 3 mm ² portions of various regions of the glove. Please refer to).

In certain embodiments of the invention, the gloves may have soft magnetic properties due to the very low coercive and residual magnetic values of the coated iron oxide nanoparticles.

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

In a further embodiment of the invention, the gloves may further comprise one or more additional layers of a polymer material free of coated iron oxide nanoparticles, and optionally the gloves are coated iron oxide nanoparticles. It further comprises at least two additional layers of particle-free polymer material, which sandwich a layer of polymer material containing coated iron oxide nanoparticles. The one or more additional layers of the polymeric material may be the same as 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 further embodiment, the glove may meet the criteria set by ASTM D6319 and EN 455.

In a second aspect of the invention, the method for making gloves according to any one of the above claims is provided, the process of which is 5 to 25 phr (eg, 8 to 20 phr) before forming the gloves. Incorporating the coated iron oxide nanoparticles of the above into a polymer material, the coated iron oxide nanoparticles exhibit one or more of the properties described above.

In embodiments of this embodiment, the polymeric material may be any suitable polymeric material that can be used to make gloves. More specifically, the polymer material may be selected from one or more of the groups consisting of synthetic rubber, natural rubber, high density polyethylene, low density polyethylene, polyamide and PVC. For example, the polymer 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 process may further comprise obtaining gloves formed from the process described above, and adding one or more additional layers of polymeric material. The one or more additional layers of the polymeric material may be the same as or different from the layer of the polymeric material incorporating the coated iron oxide nanoparticles.

The features of the invention will be more easily understood and recognized from the following detailed description when interpreted 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 the control NBR glove, FIG. 2 (b) shows the magnetically detectable NBR glove according to the present invention, and FIG. 2 (c) shows the test position in the magnetically detectable NBR glove. FIG. 3 shows NBR at various iron oxide loadings for (a) NBR-nano MAG (composite material according to the invention) thin film and (b) NBR-nano MAG gloves made from the same material. Shows the magnetization saturation of the composite material. FIG. 4 shows the magnetization saturation of NBR gloves with various filling amounts (a) 5; (b) 8; (c) 10; (d) 13; and (e) 15 phr of nanoMAG.

By incorporating nanoMAGs (coated iron oxide nanoparticles) during manufacturing, broken pieces or fragments of gloves mixed in food products can be detected by the metal detector inspection system, which means that Allows manufacturers to prevent contaminated products from reaching the market. The present invention detects and detects unwanted elements of a food processor before the final product reaches the consumer in order to maintain product safety and quality while reducing the attention of unwanted media and the risk of legal issues. We are investigating how detectable nano MAGs can help in failing.

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

In an embodiment of this embodiment, the glove is optionally measured with 20 mm ² portions 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). It may have a magnetization saturation of ~ 4.0 emu / g, etc.). The coercive force of the glove may optionally be a coercive force of 8 to 15 kA / m (eg, 8.93 to 14.33 kA / m) measured by VSM using 20 mm ² portions of the glove.

In an alternative embodiment of the invention, a magnetically detectable glove comprising at least one layer of a polymeric material containing coated iron oxide nanoparticles is provided.
Coated iron oxide nanoparticles are present in an amount of 5-25 per 100 parts of the material (eg, 8-20 per 100 parts of the material).
Gloves 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.) 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 embodiment, the coated iron oxide nanoparticles are
(I) ≧ 90% (eg ≧ 95%) may be magnetite,
(Ii) It may have a particle size of 6 to 25 nm (eg, 8 to 23 nm) as measured using a transmission electron microscope.
(Iii) may have a magnetization strength (Ms) of 62 to 75 emu / g (eg, 65 to 68 emu / g).

Magnetization saturation may be measured using a magnetic sensor (eg, metal detector, Nissin M3137, etc.) or a vibrating sample magnetometer (VSM), optionally using 20 mm ² portions of the glove. The coercive force may be measured using a VSM and optionally using 20 mm ² portions of the glove.

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

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

In addition, the raw material iron oxide nanoparticles are
Crystallinity of 85-99% (eg ≧ 90% or ≧ 95% magnetite, etc.),
Substantially spherical shape,
Polydispersity index of 0.15 to 0.25 (eg, 0.16 to 0.25, 0.17 to 0.25, etc.),
Residual magnetism of 0.19 to 1.84 emu / g (eg, 0.25 to 1.50, 0.50 to 1.00 emu / g, etc.),
Coercive force (Hc) of 3.29 to 14.71 kA / m (for example, 4.20 to 11.00 kA / m, for example, 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 the method for obtaining iron oxide nanoparticles as a raw material having these characteristics are shown below.

The polymeric material may be any suitable polymeric material that can be used to make gloves. More specifically, the polymer material may be selected from one or more of the groups consisting of synthetic rubber, natural rubber, high density polyethylene, low density polyethylene, polyamide and PVC. For example, the polymer 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 magnetic sensor can detect the entire glove. For example, at least a 3 mm × 3 mm fragment of a glove with a minimum thinness of 0.05 mm to 0.15 mm may be detectable using a suitable metal detector. For example, Nissin's 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, pentadecaneic acid, heptadecanoic acid, It may contain a coating agent selected from the group consisting of mercaptosilane and aminosilane. Specific embodiments that may be mentioned herein may relate to iron oxide nanoparticles coated with oleic acid.

The coating may form a two-layer coating on the surface of the iron oxide nanoparticles. As used herein, "two-layer coating" means a first coating layer of a coating agent in contact with iron oxide nanoparticles and a second coating layer 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). Single-layer and multi-layer coatings may be interpreted accordingly. In certain embodiments of the invention referred to herein, the coating may be in the form of two layers.

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.) on the surface of the iron oxide nanoparticles. It may be coated with a coating agent bound to.

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

Gloves 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 ^two 20 mm parts of a glove. The coercive force of the glove may optionally be a coercive force of 8 to 15 kA / m (eg, 8.93 to 14.33 kA / m) measured by VSM using 20 mm ² portions of the glove. It will be appreciated that elsewhere in the film (or film, film) provide similar results, at least for coercive force, as evidenced by the examples in which 3 mm ² provides similar results.

It is not desired to be bound by theory, and because the glove obtains soft magnetic properties due to the very low coercive force and residual magnetic value of the coated iron oxide nanoparticles used in the glove, the present invention. The particularly good results obtained with gloves can be obtained.

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

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

Gloves may further comprise one or more additional layers of coated iron oxide nanoparticles-free polymer material, and optionally gloves may include at least two layers of coated iron oxide nanoparticles-free polymer material. It further comprises an additional layer, which sandwiches a layer of polymer material containing coated iron oxide nanoparticles. It is recognized that the one or more additional layers of the polymeric material may be the same as or different from the polymeric material used to incorporate the coated iron oxide nanoparticles and may be selected from similar materials. Will be.

The gloves described above may be manufactured and coated by a process comprising incorporating 5-25 phr (eg, 8-20 phr) of coated iron oxide nanoparticles into the polymer material prior to forming the gloves. 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 gloves. More specifically, the polymer material may be selected from one or more of the groups consisting of synthetic rubber, natural rubber, high density polyethylene, low density polyethylene, polyamide and PVC. For example, the polymer 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 gloves formed from the process described above, and adding one or more additional layers of polymeric material. The one or more additional layers of the polymeric material may be the same as or different from the layer of the polymeric material incorporating the coated iron oxide nanoparticles.

Gloves are nanoMAG (coated iron oxide nanoparticles:
(I) ≧ 90% (eg ≧ 95%) magnetite,
(Ii) It has a particle size of 6 to 25 nm (eg, 8 to 23 nm) measured using a transmission electron microscope and has a particle size.
(Iii) has a magnetization strength (Ms) of 62 to 75 emu / g (for example, 65 to 68 emu / g))
The present invention will be described in more detail with respect to an embodiment of a nitrile rubber (NBR) glove incorporating the above.

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

NBR glove latex and portions thereof can be prepared from formulations containing nanoMAG wet cakes (eg, nanoMAG with a small amount of water). In certain embodiments, the nanoMAG may be fed dry and then watered to form a wet cake.

Iron oxide nanoparticles
(I) A mixture of FeCl ₂ (or its solvate) and FeCl ₃ (or its solvate) is supplied into a solvent, and the mixture is reacted with _NH4 OH to contain iron oxide nanoparticles. 1 Step to form a slurry and
(Ii) A step of separating iron oxide nanoparticles from the first slurry and
(Iii) The uncoated iron oxide nanoparticles may be formed by a process including washing with a solvent to form a wet cake of uncoated iron oxide nanoparticles.

In the separation step (ii) and the washing step (iii), the following process (a) applies a magnetic force to the first slurry to settle (or combine, settle) the iron oxide nanoparticles and decant the solvent. Steps and (b) a step of adding a solvent to form a second slurry, and then applying a magnetic force to the first slurry to precipitate iron oxide nanoparticles and decanting the solvent to form a wet cake. Optionally, the step (c) may include a step of repeating the step (b) one or more times.
In the process described above
(A) FeCl ₂ may exist as a FeCl 2.4H ₂ O solvate, FeCl ₃ may exist as a 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 the solvate used when FeCl ₃ is present as a solvate. The product) may exist in a molar ratio of 0.5: 3 to 1: 1 (for example, 0.75: 2 to 1: 1.75, 1: 1.5, etc.).

In the process described above, one or more of the following conditions may be applied.
(A) In step (i), the solvent may be water.
(B) In step (i), NH ₄ OH may be a 12 M 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 to 120 minutes, for example, 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 subjected to a treatment step to provide coated iron oxide nanoparticles. These coated iron oxide nanoparticles further contain a coating agent that coats the surface of the iron oxide nanoparticles. For example, the coating agent consists of a group consisting of hexadecanoic acid, tetradecanoic acid, dodecanoic acid, undecanoic acid, decanoic acid, stearic acid, hexanoic acid, nonanoic acid, tridecanoic acid, pentadecaneic acid, heptadecanoic acid, mercaptosilane, aminosilane and oleic acid. May be selected. Specific dressings that may be mentioned herein include oleic acid.

In order to ensure conformity between the nanoparticles and the standards required for the formation of NBR latex gloves, it may be necessary to add alkaline additives to increase the pH of the coated iron oxide nanoparticles. Thus, for example, the coating process is performed by adding various amounts of coating agent to the semi-dried nanomagnetic iron oxide nanoparticles, stirring manually, and then adding 12M NH ₄ OH (as an alkaline agent). Good (quantities listed in Table 1). The resulting suspension is ultrasonically treated with an ultrasonic generator (or sonicator, sonicator) for 1 hour and is referred to herein as "nanoMAG". It will be appreciated that the addition of alkaline agents may be used to raise the pH of the iron oxide nanoparticle slurry to a pH range suitable for incorporation in gloves. In addition, it will be recognized that any suitable alkaline agent may be used in the process.

The magnetically detectable NBR gloves of the present invention can be made using standard latex dipping techniques. Magnetically detectable NBR gloves were prepared by immersing a hand-shaped ceramic glove mold (or glove former, glove former, glove former) in a tank of coagulant and then formulating a mixture of chemicals. It can be manufactured by immersing it in a tank of liquid latex. The role of precoating the mold with a coagulant is to gel the latex to achieve accurate glove thickness, facilitating subsequent removal of magnetically detectable NBR gloves following subsequent processing. Can help. Prior to drying and curing in a heating oven, the wet latex gel on the mold is passed through a leaking tank to remove any residual hydrophilic chemicals. Then, remove the gloves from the mold and wrap them. The outer layer of the glove on the soaked mold will be the inner layer of the magnetically detectable NBR glove. The latex used to make the gloves of the present invention can contain a vulcanizing agent that cures a magnetically detectable NBR glove and produces a dry magnetically detectable NBR glove.

The magnetically detectable NBR gloves may be manufactured on a mass production line in which a plurality of magnetically detectable NBR gloves are continuously, quickly and consistently manufactured. Such techniques transport and operate a large number of glove molds into a series of chemical solutions and dispersions that make gloves. The mold is made of steel or, more particularly, ceramic, porcelain, aluminum or plastic. Gloves may be manufactured directly on a mold that is transported from one step to the next according to standard manufacturing processes.

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

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

After applying one or more laminate layers, it is preferably passed through a heated oven to dry and cure to provide the final product. Then remove the gloves either manually or by automated techniques. In accordance with the substantially automated mass production techniques described above, numerous variations may be introduced to provide additional or various desirable properties of the laminate according to the invention.

In embodiments of the invention, various NBR latex formulations have been prepared to contain 5-25 parts by weight (phr) of nanoMAG concentration per 100 total NBR latex. The unit of the component of the following formulation was based on the dry solid content of the latex set to 100 parts, and all the other components were set to the part per 100 rubber (“phr”). Nano MAG is added and mixed to form a latex to form a substantially uniform dispersion of nano MAG. Some sedimentation can occur. However, by stirring / stirring during compounding and mixing, and during immersion, continuous in the latex immersion tank so that the nanoMAG is evenly dispersed in the NBR latex layer of the porcelain-detectable NBR gloves. It is preferable to uniformly disperse the nanoMAG in the NBR latex by stirring.
Examples of various formulations are shown in Table 2.

The present invention will be described in more detail with reference to the following examples.

Protocol for measuring the metal detection ability of measuring gloves Table 3 shows the settings of Nissin's MS3137 aircraft.

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

Zetasizer Malvern's Zetasizer Nano ZS was selected to investigate the zeta potential, particle size distribution and polydispersity of IONP (iron oxide nanoparticles). It is a high performance biangle particle and molecular size analyzer with dynamic light scattering used for advanced detection of agglomeration and measurement of small or diluted samples and very low or high concentration samples. be. This technique measures the diffusion of particle movements based on Brownian motion and then transforms it into size and size distribution using the Stokes-Einstein relationship. Approximately 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 the deionized water. The zetasizer device was turned on for 30 minutes to stabilize the laser. The dispersion is then subjected to hydrodynamic size (or hydrodynamic size) and zeta potentials, respectively, in disposable polystyrene (DTS0012) and folded capillary cells (DTS1060). Infused into. The required cell was then inserted into the device to stabilize the temperature. Finally, measurements of slurry charge (or charge, charge) and particle size distribution were analyzed and the results were 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 materials scientists who attribute both image and diffraction information from a single sample. In addition, the radiation generated by the accelerated beam electrons on the sample can determine the material properties. This provides high magnification up to 1.6x where very small and minute plaid spacing can be observed. Prior to characterization of HRTEM, samples were prepared by dropping dispersed IONP onto a 300 mesh copper grid. The prepared sample was left overnight. Then, the sample prepared on the copper grid was placed in the HRTEM sample holder before being inserted into the HRTEM. Images of IONP were selected and photographed at 50,000x, 100,000x and 500,000x magnifications. The size and plaid spacing were measured by image-J. After measuring 100 IONP particles, the particle size distribution could be plotted and the plaid spacing was used to support the XRD information.

Vibrating sample magnetometer (VSM)
VSM was invented by Simon Foner (MIT scientist) in 1956 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 vibration sample magnetometer (Lakeshore-VSM7407). Approximately 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 oscillated along the z-axis perpendicular to the magnetic field (or magnetizing field) to induce a signal indicating the magnetic properties themselves. Continuous hysteresis and magnetic field of 10000 kA / m to -10000 kA / m and -10000 kA / m to 10000 kA / m were applied to confirm the magnetization saturation (Ms), coercive force (Hc) and residual magnetization (Mr) of IONP.

Preparation 1
Preparation of Iron Oxide Nanoparticles Completely dissolved aqueous solution of FeCl _{2.4H 2O} (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 in a completely dissolved aqueous solution of FeCl _{3.6H 2} O (57.42 g, 212.43 mmol, in 100 mL of H ₂ O; FeCl _{2.4H 2} O / FeCl _{3.6H 2} O A molar ratio of 1: 1.5) was added in succession. Ammonia hydroxide (12M, 1000 mL) was then added to the 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 agglomeration.

Preparation 2
Oleic acid (0.4 g) was added to the semi-dried nanomagnetic iron oxide nanoparticles and stirred manually, followed by the addition of 12 M NH ₄ OH (amounts shown in Table 4). The resulting suspension was treated with sonic waves for 1 hour using a sonic generator.

The nanoMAG materials used in the following examples were prepared using the process described above, but the quantities were scaled up proportionally.

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

First, the mixing tank was thoroughly cleaned with a brush and detergent to ensure no contamination during the compounding process. The NBR latex was filtered and transferred to a mixing tank. The latex was stirred at a stirring speed of 50 rpm for 30 minutes. After that, the pH of the latex was adjusted to pH 9.6 to 9.7. Next, sodium dodecylbenzene sulfonate (SDBS) was slowly added to the latex and stirring was continued for 1 hour. The pH of the compound latex was measured again and adjusted to pH 9.6 to 9.7. The remaining chemicals except Aquawax (or aqueous wax, Aquawax) and nanoMAG were slowly added to the latex compound and stirred for an additional hour. Then, the stirring speed was reduced to 30 rpm and the mixture was left overnight. At this stage, 5, 8, 10, 13 and 15 phr 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 of calcium nitrate (CN), 25 g of perfluorinated carboxylic acid (PFCA; powder-free mold release agent) and 2 g of nonionic wetting agent (Teric 320) were added to 1487.32 g of water at 60 ° C. The resulting mixture was poured into a coagulation tank to prepare a coagulant used to promote coagulation of the latex on the surface of the mold. The compounded latex produced as described above was filtered and poured into an immersion tank. Thoroughly clean the mold with soap and brush to prevent oily materials or residual latex that can cause defects in the final film / gloves produced from remaining on the mold (eg, glove mold or template) and in large quantities. Rinse with excess water.

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

The thickness of 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).

2 (a) and 2 (b) show the results for magnetically detectable NBR gloves with and without nanoMAG (b) and (a). It was found that the magnetically detectable NBR gloves shown in FIG. 2 (b) did not have nano-MAG aggregation.

FIG. 2 (c) shows various test positions on magnetically detectable NBR gloves made according to the process described above. Tables 6-10 show the magnetic properties of the 5, 8, 10, 13 and 15 phr nanoMAGs at various positions on the magnetically detectable NBR gloves, respectively.

As shown in these tables, the location of the fingertips appears to have higher magnetic strength and the location of the wrist appears to have lower magnetic strength compared to other locations. This is because the film thickness in the fingertip region is usually thicker than in the other regions, while the wrist region is usually thinner, which makes it appear that the amount of nanoMAG material is evenly distributed throughout the film. Indicates that.

FIG. 3 shows the saturation magnetization of the magnetically detectable NBR film (a) and NBR glove (b) for various filling amounts (0 to 15 phr) of the nanoMAG slurry. NBR-nano MAG gloves were produced by the process described above, and NBR-nano MAG thin film was produced using the process described above using a square mold. It was observed that the magnetization saturation increased linearly as the iron oxide filling amount increased from 0 to 15 phr. However, the saturation magnetization of the NBR-nano MAG thin film was higher than that of the NBR-nano MAG glove, probably due to the thickness of the glove. The product exhibits very low coercive force and residual magnetism, and the magnetic strength exhibits superparamagnetic properties. Therefore, the product contains magnetite particles with soft magnetic properties.

FIG. 4 shows the hysteresis curves of gloves / thin films with various phr fillings of nanomag. As shown in FIG. 4, as the filling amount of nanoMag increases, there is a significant increase in saturation magnetization observed in gloves / thin films ((a)-(e), D1 is the batch of formulated latex used. means).

Example 3
Numerous gloves with nano MAGs of 5, 8, 10, 13 and 15 phr were produced using the processes and formulations described above, except that the gloves were provided using a single dip in latex. Then, these gloves were tested for the above-mentioned magnetic detection ability. The results are shown in Table 11 below.

Nano MAGs with a phr of 5 do not seem to work at the thicknesses described, but it will be recognized that a phr of 5 will work if a thicker glove film is formed. In addition, it will be recognized that thinner glove films will also work with increased amounts of nanoMAG (phr).

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

The physical properties of the gloves were tested before and after aging, 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" means an American Society for Testing and Materials standards and associated protocol. "EN" means European standards and related protocols.

Claims (22)

A magnetically detectable glove comprising at least one layer of a polymeric material containing coated iron oxide nanoparticles.
The coated iron oxide nanoparticles are present in an amount of 5-25 per 100 parts of the polymer material.
The coated iron oxide nanoparticles
(I) ≧ 90% magnetite,
(Ii) It has a particle size of 6 to 25 nm measured using a transmission electron microscope and has a particle size.
(Iii) It has a magnetization strength (Ms) of 62 to 75 emu / g and has a magnetization strength (Ms).
The glove has a magnetization saturation of 1 emu / g to 12 emu / g and / or a coercive force of 8 to 15 kA / m, both measured using 20 mm ² portions of the glove.
The group in which the coated iron oxide nanoparticles consist of oleic acid, hexadecanoic acid, tetradecanoic acid, dodecanoic acid, undecanoic acid, decanoic acid, hexanoic acid, nonanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, mercaptosilane and aminosilane. Gloves coated with a coating agent selected from. A magnetically detectable glove comprising at least one layer of a polymeric material containing coated iron oxide nanoparticles.
The coated iron oxide nanoparticles are present in an amount of 5-25 per 100 parts of the polymer material.
The glove has a magnetization saturation of 1 emu / g to 12 emu / g and / or a coercive force of 8 to 15 kA / m, both measured using 20 mm ² portions of the glove.
The coated iron oxide nanoparticles
(I) ≧ 90% magnetite,
(Ii) It has a particle size of 6 to 25 nm measured using a transmission electron microscope and has a particle size.
(Iii) It has a magnetization strength (Ms) of 62 to 75 emu / g and has a magnetization strength (Ms).
The group in which the coated iron oxide nanoparticles consist of oleic acid, hexadecanoic acid, tetradecanoic acid, dodecanoic acid, undecanoic acid, decanoic acid, hexanoic acid, nonanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, mercaptosilane and aminosilane. Gloves coated with a coating agent selected from. The glove according to claim 1 or 2, wherein the polymer material is selected from one or more of the groups consisting of synthetic rubber, natural rubber, high density polyethylene, low density polyethylene, polyamide and PVC. The glove according to claim 3, wherein the polymer material is styrene butadiene rubber, polychloroprene rubber, synthetic polyisoprene rubber, polyurethane rubber, or more specifically, nitrile rubber. The invention according to any one of claims 1 to 4, wherein the coated iron oxide nanoparticles are distributed throughout the layer of the polymer material so that the entire glove can be detected by the magnetic sensor. Gloves. The glove according to any one of claims 1 to 5, wherein a fragment of at least 3 mm × 3 mm of a glove having a minimum thinness of 0.05 mm to 0.15 mm can be detected. The glove according to any one of claims 1 to 6, wherein the coated iron oxide nanoparticles are coated with oleic acid. The glove according to any one of claims 1 to 7, wherein the coating agent forms a two-layer coating on the surface of the iron oxide nanoparticles. Any one of claims 1-8, wherein the coated iron oxide nanoparticles are coated with a coating agent bonded to the surface of the iron oxide nanoparticles at a weight / weight ratio greater than 0.2: 1. Gloves described in section. The glove according to any one of claims 1 to 9, wherein the iron oxide nanoparticles have a polydispersity index of 0.13 to 0.25. The iron oxide nanoparticles
Residual magnetism of 0.80 to 1.07 emu / g and / or coercive force (Hc) of 6.47 to 8.5 kA / m
The glove according to any one of claims 1 to 10. The coated iron oxide nanoparticles
(I) have a zeta potential of -45 to -55 mV and / or (ii) have a magnetic strength that is reduced by 1% to 6% when subjected to oxidation, and / or (iii) 20 days. The glove according to any one of claims 1 to 11, which has water stability or water / latex medium stability from 1 to 100 days. The glove according to any one of claims 1 to 12, wherein the glove has soft magnetic properties due to the very low coercive force and residual magnetic value of the coated iron oxide nanoparticles. The gloves
(A) Thickness of 0.05-0.11 mm measured according to ASTM D3767 and / or
The glove according to any one of claims 1 to 13, which has (b) a tensile strength of 23.3 to 29.7 MPa according to ASTM D412 and / or (c) an elongation of 558 to 660% measured according to ASTM D412. .. 14. The glove according to claim 14, wherein the glove further comprises one or more additional layers of a polymer material that does not contain coated iron oxide nanoparticles. The one or more additional layers of the polymer material are at least two additional layers of the polymer material that do not contain coated iron oxide nanoparticles, and the layer is a polymer that contains the coated iron oxide nanoparticles. The glove according to claim 15, which sandwiches the layer of the material. The glove according to any one of claims 1 to 16, wherein the glove satisfies the criteria set by ASTM D6319 and EN 455. The method for producing a glove according to any one of claims 1 to 17, wherein the process incorporates 5 to 25 phr of coated iron oxide nanoparticles into the polymer material before forming the glove. Including the process
The coated iron oxide nanoparticles
(I) ≧ 90% magnetite,
(Ii) It has a particle size of 6 to 25 nm measured using a transmission electron microscope and has a particle size.
(Iii) A method for manufacturing a glove having a magnetization strength (Ms) of 62 to 75 emu / g. The method for producing a glove according to claim 18, 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 method for producing a glove according to claim 19, 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 the polymer material to the polymer material incorporating the coated iron oxide nanoparticles.
The glove according to any one of claims 18 to 20, wherein the one or more additional layers of the polymer material may be the same as or different from the layer of the polymer material incorporating the coated iron oxide nanoparticles. Manufacturing method. The one or more additional layers of the polymer material are at least two additional layers of the polymer material that do not contain coated iron oxide nanoparticles, and the layer is a polymer that contains the coated iron oxide nanoparticles. The method for manufacturing a glove according to claim 21 , wherein the layer of the material is sandwiched.

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