WO2014200047A1 - 手袋及びその製造方法 - Google Patents

手袋及びその製造方法 Download PDF

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Publication number
WO2014200047A1
WO2014200047A1 PCT/JP2014/065540 JP2014065540W WO2014200047A1 WO 2014200047 A1 WO2014200047 A1 WO 2014200047A1 JP 2014065540 W JP2014065540 W JP 2014065540W WO 2014200047 A1 WO2014200047 A1 WO 2014200047A1
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Prior art keywords
glove
particles
magnetic
magnetic particles
mass
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Ceased
Application number
PCT/JP2014/065540
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English (en)
French (fr)
Japanese (ja)
Inventor
憲秀 榎本
太一 小川
大輔 平馬
カム ホン クアン
ムン レオン クアン
ユー ジン クアン
メイ リン チア
ザイディ ビン マット サーター モハド
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Midori Anzen Co Ltd
HARTALEGA Sdn Bhd
Original Assignee
Midori Anzen Co Ltd
HARTALEGA Sdn Bhd
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=52022337&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2014200047(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Midori Anzen Co Ltd, HARTALEGA Sdn Bhd filed Critical Midori Anzen Co Ltd
Priority to EP14811027.3A priority Critical patent/EP3009021B1/en
Priority to CN201480044711.7A priority patent/CN105451584B/zh
Priority to DK14811027.3T priority patent/DK3009021T3/da
Priority to JP2015522848A priority patent/JP6546086B2/ja
Priority to AU2014279085A priority patent/AU2014279085B2/en
Priority to US14/898,412 priority patent/US9808039B2/en
Priority to MYPI2015704537A priority patent/MY186163A/en
Publication of WO2014200047A1 publication Critical patent/WO2014200047A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00—Gloves
    • A41D19/0055—Plastic or rubber gloves
    • A41D19/0082—Details
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00—Gloves
    • A41D19/0055—Plastic or rubber gloves
    • A41D19/0058—Three-dimensional gloves
    • A41D19/0062—Three-dimensional gloves made of one layer of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L13/00—Compositions of rubbers containing carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter

Definitions

  • the present invention relates to a glove, and more particularly to a glove detected by a metal detector and a method for manufacturing the glove.
  • Rubber gloves or plastic gloves are widely used in various industries such as food industry, electronic parts manufacturing industry, pharmaceutical industry, and medical industry. In such an application, it is a problem that the glove is broken and becomes a small glove piece, and this glove piece is mixed into a product or packaging. In particular, in the food industry, it is important to detect contamination of glove pieces in order to manufacture food safely and in large quantities.
  • a method of detecting a piece of glove mixed in a product or the like there is a method of detecting a piece of glove containing a magnetic material by premixing a glove with a magnetic material and measuring the product or the like with a metal detector. is there.
  • a product or the like can be measured by a belt conveyor type metal detector, and a piece of glove mixed in the product or the like can be detected.
  • Patent Document 1 proposes a glove composed of a glove body having a thickness of 0.01 to 3 mm formed from rubber, a synthetic resin or a synthetic resin film, in which black iron oxide powder is mixed into the glove body.
  • black iron oxide powder of 0.1 to 1 ⁇ m or less is blended at 20% by mass or more with respect to rubber or the like.
  • Patent Document 2 proposes a magnetically detectable latex article that includes chromium oxide dispersed throughout the cured latex layer and the cured tex layer.
  • Patent Document 1 since the amount of black iron oxide powder is large, it is possible to detect pieces of gloves using a metal detector or the like. However, when the black iron oxide powder is mixed excessively, the mechanical characteristics and feeling of use of the glove may be lowered. Further, black iron oxide powder of 0.1 to 1 ⁇ m or less is simply added to the glove.
  • Patent Document 2 although the particle size of the chromium oxide raw material of the example is described as 0.30 ⁇ m to 15.00 ⁇ m, the shape of individual particles in the glove has not been studied. In Patent Document 2, chromium oxide is simply added and stirred in latex to prepare a dispersion (paragraph 0018).
  • an object of the present invention is to reduce the minimum detection volume of the glove piece by the metal detector.
  • One aspect of the present invention is a glove having a single layer or a plurality of layers formed of rubber or resin, and including magnetic particles in all or part of the layer, wherein the magnetic particles are The amount of the magnetic particle is 0.2% by mass or more and less than 40% by mass with respect to the entire film, and the magnetic particle is a glove including secondary particles in which primary particles are aggregated.
  • a glove comprising a plurality of rubber layers or resin layers using an emulsion, wherein the magnetic particles are 0.2 mass% or more and less than 40 mass% with respect to the entire glove film, and the secondary particles are aggregated with primary particles. It is the manufacturing method of a glove including the process to produce.
  • the minimum detection volume of the glove piece by the metal detector can be reduced.
  • FIG. 1 is an electron micrograph of a glove cross section of Example 5.
  • FIG. FIG. 2 is an electron micrograph of a glove cross section of Comparative Example 3.
  • FIG. 3 is an electron micrograph of a glove cross section of Example 9.
  • a glove according to an embodiment of the present invention is a glove having a single layer or a plurality of layers of a film formed of rubber or resin, all or part of the film including magnetic particles, wherein the magnetic particles are: It is 0.2 mass% or more and less than 40 mass% with respect to the whole glove,
  • the magnetic particle is characterized by including the secondary particle which the primary particle aggregated.
  • the sensitivity of detecting a glove piece by a metal detector can be increased.
  • contamination of foreign matters becomes a problem, but according to this embodiment, it is possible to detect smaller pieces of gloves with a metal detector, and to prevent the pieces of gloves from being mixed into food or packaging. Can do.
  • natural rubber and synthetic rubber can be used as rubber, and specifically, natural rubber, nitrile butadiene rubber (NBR), carboxylated NBR (X-NBR), isoprene rubber, chloroprene.
  • natural rubber nitrile butadiene rubber (NBR), carboxylated NBR (X-NBR), isoprene rubber, chloroprene.
  • NBR nitrile butadiene rubber
  • X-NBR carboxylated NBR
  • isoprene rubber chloroprene
  • chloroprene chloroprene
  • examples thereof include rubber, butyl rubber, butadiene rubber, silicone rubber, fluorine rubber, urethane rubber, styrene butadiene rubber (SBR), and polychloroprene. These can be used alone or in combination of two or more.
  • the unvulcanized rubber preferably has a Mooney viscosity (ML1 + 4 (100 ° C.)) of 30 to 200, which is a measure of its molecular weight. If this Mooney viscosity is less than the lower limit, there is a concern about migration (bleed) to the surface of the glove, and if this upper limit is exceeded, the flexibility of the glove may be insufficient.
  • Mooney viscosity ML1 + 4 (100 ° C.)
  • examples of the resin include polyvinyl chloride resin, polyethylene resin, polyacrylic resin, polyurethane resin, and polypropylene resin. These can be used alone or in combination of two or more.
  • the resin preferably has a styrene-converted mass average molecular weight of 10,000 to 1,000,000, more preferably 15,000 to 800,000. If this molecular weight is less than the lower limit, there is a concern about migration (bleed) to the glove surface, and if this upper limit is exceeded, the flexibility of the glove may be insufficient.
  • the magnetic particles according to this embodiment preferably have a saturation magnetic moment per unit mass of 50 G ⁇ cm 3 / g, 50 A / m ⁇ kg or more, or 6.28 ⁇ 10 ⁇ 5 Wb ⁇ m / kg or more.
  • ferrite As magnetic particles, ferrite, pure iron, chromium oxide, cobalt, or the like can be used.
  • ferrite include nickel ferrite, manganese ferrite, maghemite, magnetite (FeFe 3+ 2 O 4 ), manganese / zinc ferrite (Mn / ZnFe 2 O 4 ), nickel / zinc ferrite (Ni / ZnFe 2 O 4 ), and the like. Can do. These can be used alone or in combination of two or more.
  • Magnetite can be preferably used from the viewpoint of stability, safety, and availability.
  • a glove conforming to the Japanese food hygiene law can be manufactured, and in particular, a glove that can be used with confidence in the food industry can be manufactured.
  • the magnetic particles preferably include secondary particles in which primary particles are aggregated.
  • Aggregation is a form in which a plurality of primary particles gather to form one aggregate with a plurality of primary particles.
  • the form of the secondary particles in which the primary particles are aggregated can be confirmed by a scanning electron microscope (SEM), and one particle, that is, a plurality of primary particles are gathered to form one aggregate, that is, an aggregate. Observed.
  • a glove in which large magnetic particles are uniformly distributed can be manufactured.
  • a magnetic particle dispersion is produced, if large magnetic particles are suddenly dispersed and mixed in a solvent, the magnetic particles settle and are not uniformly dispersed in the solvent.
  • the primary magnetic particles aggregate in the mixing process to form secondary magnetic particles, thereby obtaining a magnetic particle dispersion in which large magnetic particles are uniformly dispersed. be able to. That is, when the magnetic particles are present in the form of secondary particles in which the primary particles are aggregated in the glove film, the distribution of the magnetic particles in the film can be made more uniform.
  • the volume ratio of the particles whose secondary particles have a particle diameter exceeding 1 ⁇ m is preferably 20% by volume or more based on the total volume of the whole particles.
  • the volume ratio of the particles having a particle diameter of the secondary particles exceeding 1 ⁇ m is preferably 30% by volume or more, more preferably 35% by volume or more, and further preferably 40% by volume with respect to the total volume of the whole particles. % Or more.
  • the volume ratio of the particles whose particle diameter exceeds 2 ⁇ m is 20% by volume or more with respect to the total volume of the whole particles. It is possible to increase the magnetic sensitivity of the metal detector and increase the detection sensitivity of the metal detector. Furthermore, since the volume ratio of the secondary particles of the magnetic particles having a particle diameter exceeding 1 ⁇ m is 20% by volume or more with respect to the total volume of the whole particles, the magnetic particles are contained in the glove with a small amount of magnetic particles. Evenly blended, the magnetic characteristics of the glove can be improved and the detection sensitivity of the metal detector can be increased.
  • the upper limit of the volume ratio of the particles having a particle size of the secondary particles exceeding 1 ⁇ m is not particularly limited, and may be 100% by volume or less, considering that small particles are mixed depending on the particle size distribution. In general, it is preferably 90% by volume or less.
  • the secondary particle size of the magnetic particles can be measured by the following method. First, secondary particles are observed on a cross section obtained by cutting a glove using a scanning electron microscope (SEM). Here, the secondary particles are observed as one particle, that is, an aggregate in which two or more primary particles are observed. Next, the major axis and minor axis of the observed secondary particles are measured. Then, the diameter of a true sphere having the same volume as the secondary particles can be calculated, and this diameter can be used as the secondary particle diameter. Measurement of the volume ratio of particles having a particle diameter of secondary particles exceeding 1 ⁇ m can be performed by the following method.
  • the cross-section of the glove was observed using a scanning electron microscope (SEM) so that 200 to 700 secondary particles were included in a predetermined range, and the diameters of these 200 to 700 secondary particles were determined. Obtained by the method described above.
  • the volume ratio of the particles whose secondary particle diameter exceeds 1 ⁇ m can be obtained as the ratio of the volume of the secondary particles exceeding 1 ⁇ m to the total volume of 200 to 700 secondary particles. .
  • the average particle diameter of primary particles of magnetic particles is preferably 1 ⁇ m or less. Further, the average particle diameter is the number average particle diameter unless otherwise specified (the same applies hereinafter).
  • the magnetic particles can be uniformly mixed in the glove as a whole. That is, in the glove manufacturing method, magnetic particles can be uniformly dispersed in the raw material, and the magnetic particles can be uniformly blended in the resulting glove.
  • the average particle size of the primary particles of the magnetic particles is more preferably 0.8 ⁇ m or less, still more preferably 0.6 ⁇ m or less, and even more preferably 0.4 ⁇ m or less.
  • the average particle diameter of the primary particles of the magnetic particles decreases, the specific surface area increases and the surface of the magnetic particles may be deactivated by oxidation.
  • the average particle diameter of the primary particles of the magnetic particles is preferably 0.001 ⁇ m or more, more preferably 0.005 ⁇ m or more, and further preferably 0.01 ⁇ m or more.
  • the primary particle size of the magnetic particles is measured by measuring 200 to 700 primary particle sizes in the same manner as the measurement of the secondary particle size described above, and averaging these on the basis of the number. It can be carried out. In observation with a scanning electron microscope (SEM), primary particles are observed as one particle.
  • SEM scanning electron microscope
  • the content of the magnetic particles is 0.2% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.5% by mass or more with respect to the entire glove film. This increases the saturation flux density of the entire glove so that smaller glove pieces can be detected by the metal detector.
  • the content of the magnetic particles is less than 40% by mass, more preferably 30% by mass or less, and further preferably less than 20% by mass with respect to the entire glove film.
  • ferrite particles are contained in an amount of 10% by mass or more, more preferably 70% by mass or more based on the entire magnetic particles.
  • the ferrite is magnetite.
  • the magnetite is preferably contained in an amount of 50% by mass or more, more preferably 80% by mass or more, based on the entire glove magnetic particles.
  • the content and composition ratio of magnetic particles can be determined from the ratio of the amount of magnetic particles to the total amount of non-volatile content (solid content) in the raw materials to be blended in the glove manufacturing process.
  • the content of magnetic particles can be determined by measuring the residual amount of magnetic particles in the glove using a high frequency plasma emission analysis (ICP-AES) apparatus.
  • ICP-AES high frequency plasma emission analysis
  • composition ratio of the magnetic particles can be measured by using X-ray diffraction analysis (XRD).
  • a sample piece obtained by carbonizing a glove at 400 ° C. in a nitrogen atmosphere may be used.
  • This sample piece can be measured under the following conditions using “RINT2000” manufactured by Rigaku Corporation as a measuring device for X-ray diffraction analysis.
  • Divergence / scattering slit 1 deg.
  • Light receiving slit 0.3 mmsw.
  • the glove according to the present embodiment may contain other optional components as long as the effects of the present invention are not impaired.
  • the arbitrary component added to a raw material can be mentioned.
  • the total amount of these optional components can usually be blended at 25% by mass or less with respect to the entire glove.
  • the minimum detection volume of the glove piece by the metal detector is preferably 40 mm 3 or less, more preferably 38 mm 3 or less, and further preferably 36 mm 3 or less.
  • the glove piece can be detected by the metal detector even with a smaller amount of magnetic particles, the size of the detectable glove piece can be further reduced.
  • the lower limit value of the minimum detection volume by the metal detector of the glove piece can be usually 0.50 mm 3 or more.
  • the minimum detection volume of the glove piece by the metal detector can be measured by the following method.
  • Gloves are cut into various sizes to make glove pieces, and whether each glove piece is detected by a metal detector is measured. And let the volume of the glove piece of the minimum size detected by a metal detector be a minimum detection volume.
  • metal detectors examples include “duw-h KD8112BW” manufactured by Anritsu Industrial Equipment Systems Co., Ltd. and “MS-3137A-25HI-100” manufactured by Nissin Electronics Industry Co., Ltd. Each of these has a setting detection sensitivity of an iron ball diameter of ⁇ 0.5 mm.
  • the size of the glove piece detected as being equivalent to an iron ball having a diameter of 0.5 mm in a metal detector is, according to this embodiment, when the amount of magnetic particles relative to the entire glove is 15% by mass, .08 mm and 3 mm square glove pieces, that is, glove pieces having a volume of 0.7 mm 3 .
  • the size of the glove piece detected by the metal detector as being equivalent to an iron ball having a diameter of 0.5 mm is 0. 03 mm and 5.5 mm square glove pieces, that is, the volume of the glove pieces is 0.9 mm 3 .
  • the saturation magnetic flux density of the gloves is preferably 1 gauss or more, more preferably 4 gauss or more. This allows smaller glove pieces to be detected by the metal detector. In the present embodiment, the saturation magnetic flux density of the glove can be increased even with a smaller amount of magnetic particles.
  • the saturation magnetic flux density of the gloves is preferably 220 gauss or less, more preferably 200 gauss or less. If the blending amount of the magnetic particles is excessively increased in order to increase the saturation magnetic flux density, the mechanical characteristics of the glove may be deteriorated, which can be prevented.
  • the saturation magnetic flux density of the glove can be measured with a sample vibration type magnetometer (VSM). Specifically, using “VSM-5-15 type” manufactured by Toei Kogyo Co., Ltd., measuring at room temperature with a magnetic calibration of Ni (nickel) and Gd 2 O 3 (gadolinium oxide) and a measuring magnetic field of 10 kOe. Can do.
  • VSM-5-15 type manufactured by Toei Kogyo Co., Ltd.
  • the tensile strength of the glove is preferably 20 MPa or more, more preferably 21 MPa or more, and further preferably 22 MPa or more.
  • the tensile elongation at break of the glove is preferably 400% or more, more preferably 410% or more, and further preferably 415% or more.
  • the 100% modulus of the glove is preferably 5.5 MPa or less, and more preferably 5.2 MPa or less.
  • the mechanical properties and feeling of use of the glove can be enhanced.
  • the amount of magnetic particles in the glove can be adjusted appropriately, and mechanical characteristics and a feeling of use equivalent to those of a glove not containing magnetic particles can be obtained.
  • the dumbbell shape No. 5 can be measured at a tensile speed of 500 mm / min.
  • the thickness of the glove is preferably 0.20 mm or less, more preferably 0.15 mm or less, and still more preferably 0.10 mm or less.
  • detection with a metal detector is possible with a smaller amount of magnetic particles. Therefore, even if the thickness of the glove is reduced to 0.20 mm or less, the detection sensitivity can be maintained.
  • the thickness of the glove is preferably 0.05 mm or more, and more preferably 0.07 mm or more.
  • the method for producing a glove according to an embodiment of the present invention includes a step of dispersing a magnetic particle having an average primary particle size of 1 ⁇ m or less in a solvent to prepare a magnetic particle dispersion, and an emulsion containing rubber or resin.
  • Adding a magnetic particle dispersion to produce a magnetic particle-containing emulsion in which the magnetic particles are 0.2% by weight or more and less than 80% by weight with respect to the total solid content, and a single layer or different using the magnetic particle-containing emulsion A secondary layer in which a plurality of rubber layers or resin layers are formed using a magnetic particle-containing emulsion having a composition, and the magnetic particles are 0.2 mass% or more and less than 40 mass% with respect to the entire glove film, and the primary particles are aggregated.
  • the method includes the step of producing a glove containing particles.
  • magnetic particles having an average primary particle diameter of 1 ⁇ m or less are dispersed in a solvent to produce a magnetic particle dispersion.
  • the magnetic particles are as described above.
  • the primary particles of the magnetic particles are aggregated to form aggregates in the dispersion.
  • the volume ratio of particles having a particle diameter exceeding 1 ⁇ m is preferably 20% by volume or more based on the total volume of the particles. It is considered that the agglomerates are blended as magnetic particles of secondary particles having a particle diameter in the above range in the glove while maintaining the shape.
  • the magnetic particles as the raw material may have an average primary particle diameter of 1 ⁇ m or less, more preferably 0.8 ⁇ m or less, still more preferably 0.6 ⁇ m or less, and even more preferably 0.4 ⁇ m or less. is there.
  • the magnetic particles as a raw material preferably have an average primary particle diameter of 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more.
  • the primary particles of the magnetic particles as the raw material do not aggregate to form secondary particles.
  • the aggregates formed in the dispersion maintain the shape and size of the aggregates even after the production of gloves.
  • the particle diameter of the aggregate formed in the dispersion substantially corresponds to the particle diameter of the secondary particles described above.
  • the solvent for the magnetic particle dispersion is preferably an aqueous solvent, preferably an aqueous dispersion, and may optionally contain a water-soluble organic solvent.
  • the magnetic particles are preferably contained in an amount of 10% by mass or more, more preferably 12% by mass or more, based on the entire magnetic particle dispersion.
  • the magnetic particles are preferably contained at 90% by mass or less, more preferably 85% by mass or less, with respect to the entire magnetic particle dispersion. In this range, the dispersibility of the magnetic particles in the solvent can be increased, and the abundance ratio of the secondary particles existing in the glove by controlling the size of the aggregates in the dispersion is within the above range. Can be obtained at
  • a surfactant can be added as a dispersant to the magnetic particle dispersion.
  • the surfactant include carboxylate, sulfonate, polyacrylate, phosphate, polyphosphate ester, polymerized alkylarylsulfonate, polymerized sulfonated naphthalene, polymerized naphthalene / Anionic surfactants such as formaldehyde condensation polymers; Nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol alkyl esters, polyethylene glycol fatty acid amides; Cationic surfactants such as alkyltrimethylammonium salts and benzalkonium salts; and amphoteric surfactants such as N, N-dimethyl-N-alkyl-N-carboxyammonium betaine and N, N-dialkylaminoalkylenecarboxylate
  • an anionic surfactant can be used.
  • Preferred examples of the surfactant include polyethylene glycol alkyl ethers, sulfonates such as alkylbenzene sulfonates and aliphatic sulfonates, and polyacrylates.
  • the surfactant can be blended in an amount of 0.1 to 5.0 parts by weight, more preferably 0.2 to 4.0 parts by weight with respect to 100 parts by weight of the solid content contained in the entire magnetic particle dispersion. It is.
  • a colorant and a pigment may be added to the magnetic particle dispersion.
  • caramel pigments natural pigments such as gardenia blue, and synthetic colorants such as indigo carmine (blue No. 2) and rose bengal (red No. 105) can be used.
  • the colorant can be blended in an amount of 1.0 to 20.0 mass%, more preferably 2.0 to 15.0 mass%, based on the entire magnetic particle dispersion. Further, the colorant is preferably contained in an amount of 0.1 to 1.0% by mass, more preferably 0.2 to 0.8% by mass with respect to the entire glove after the production of the glove.
  • the pigment examples include white pigments such as TiO 2 and zinc oxide, red pigments such as red lead and iron oxide, and blue pigments such as ultramarine blue and phthalocyanine blue.
  • the pigment can be blended in an amount of 10 to 90% by mass, more preferably 15 to 80% by mass, based on the entire magnetic particle dispersion. Further, the pigment is preferably contained in an amount of 1.0 to 5.0% by mass, more preferably 1.5 to 4.5% by mass with respect to the entire glove after the production of the glove.
  • the above-mentioned components can be mixed at once or divided and can be arbitrarily stirred.
  • the magnetic particles are sufficiently dispersed in the dispersion.
  • Each component can be added to the solvent sequentially or simultaneously.
  • various usual aqueous solution stirring methods can be used.
  • the stirring time can usually be set at 0.3 to 2.0 hours, preferably 0.5 to 1.5 hours.
  • a magnetic particle dispersion is added to an emulsion containing rubber or resin to produce a magnetic particle-containing emulsion.
  • the rubber or resin contained in the emulsion is as described above.
  • the emulsion containing rubber or resin is preferably a water-based emulsion and may optionally contain a water-soluble organic solvent.
  • the magnetic particles may be 0.2% by mass or more based on the total solid content of the magnetic particle-containing emulsion. Preferably it is 0.3 mass% or more, More preferably, it is 0.5 mass% or more. On the other hand, it is preferably less than 80% by mass, and more preferably 70% by mass or less.
  • an emulsion containing rubber that is, rubber latex
  • various additives such as a vulcanizing agent, a vulcanization accelerator, a vulcanization acceleration aid, and a dispersant are optionally added to the rubber latex to obtain a magnetic particle dispersant.
  • a vulcanizing agent such as a vulcanizing agent, a vulcanization accelerator, a vulcanization acceleration aid, and a dispersant.
  • a dispersant such as a vulcanizing agent, a vulcanization accelerator, a vulcanization acceleration aid, and a dispersant are optionally added to the rubber latex to obtain a magnetic particle dispersant.
  • This rubber latex containing magnetic particles is attached to a glove mold, and the glove mold is dried and heated to vulcanize the rubber, thereby providing a glove.
  • the rubber latex preferably has a rubber solid content of 12 to 60% by mass, more preferably 40 to 50% by mass.
  • Sulfur can be used as the vulcanizing agent.
  • the vulcanizing agent is preferably 0.5 to 4.5 parts by mass with respect to 100 parts by mass of rubber solids in the rubber latex.
  • vulcanization accelerator examples include dithiocarbamate, tyrium, thiazole compounds, and the like.
  • a bivalent metal oxide can be used preferably.
  • the divalent metal oxide include zinc oxide, calcium oxide, and magnesium oxide.
  • the rubber accelerator is preferably 0.2 to 2.5 parts by mass with respect to 100 parts by mass of rubber solids.
  • the emulsifier or dispersant those mentioned above for the magnetic particle dispersion can be used.
  • the emulsifier or dispersant in the rubber latex is preferably one that does not react with the dispersant in the magnetic particle dispersion to form an aggregate. More preferably, the same dispersant is used for the rubber latex and the magnetic particle dispersion.
  • the dispersant is preferably 2 to 4 parts by mass with respect to 100 parts by mass of rubber solids.
  • an emulsion containing a resin that is, a resin emulsion
  • various additives such as a dispersant are optionally added to the resin emulsion, and a magnetic particle dispersant is added.
  • the magnetic particle-containing resin emulsion is attached to a glove mold, and the glove mold is dried and heated to solidify the resin, thereby providing a glove.
  • the resin emulsion preferably has a resin solid content of 12 to 60% by mass, more preferably 40 to 50% by mass.
  • the dispersant added to the resin emulsion is the same as the rubber latex described above.
  • the rubber latex and resin emulsion may further contain other optional components.
  • optional components include anti-aging agents such as phenols and amines, and fillers such as kaolin and calcium carbonate.
  • anti-aging agents such as phenols and amines
  • fillers such as kaolin and calcium carbonate.
  • These other optional components can be blended in an amount of usually 10% by mass or less based on the entire rubber latex and / or resin emulsion.
  • the above-mentioned optional components may be further added.
  • a release agent such as paraffin wax or vegetable wax can be added. These release agents also function as antiaging agents. These release agents can be blended in an amount of usually 5% by mass or less based on the entire magnetic particle-containing emulsion.
  • the rubber latex and the resin emulsion are preferably alkaline having a pH of 8 or more, more preferably 9 to 11. Potassium hydroxide or ammonia may be added as a pH adjuster.
  • the solid content of the magnetic particle-containing emulsion can usually be 10 to 85% by mass, more preferably 12 to 80% by mass.
  • a glove is produced using the magnetic particle-containing emulsion.
  • the glove is preferably produced by a dipping method (dipping method).
  • a dipping method a direct dipping method, an adhesion dipping method, a heat-sensitive dipping method, or the like can be used.
  • a glove mold made of wood, metal, or ceramic in the shape of a hand is dipped in an emulsion, adhered to the surface of the glove mold, dried and vulcanized to produce a glove. be able to.
  • an anode method using a coagulant As the adhesion dipping method, an anode method using a coagulant, a Teague method, a reversal method, or the like can be used.
  • a coagulant As the coagulant, calcium nitrate, calcium chloride, magnesium chloride or the like can be used.
  • the glove mold is immersed in a coagulant to adhere the coagulant to the surface of the glove mold, and then the glove mold is immersed in the emulsion to adhere it to the surface of the glove mold, dried and dried.
  • Gloves can be produced by vulcanization.
  • a glove mold is immersed in an emulsion and adhered to the surface of the glove mold, and then the glove mold is immersed in a coagulant to gel the emulsion on the surface of the glove mold, and then dried and dried.
  • Gloves can be produced by vulcanization.
  • a glove can be produced by alternately immersing a glove mold in a coagulant and an emulsion, followed by drying and vulcanization. This method is suitable for the production of thick gloves and gloves with a slow gelation emulsion.
  • a heat-sensitive coagulant is added to the emulsion described above, a heated glove mold is immersed in the emulsion, and this is adhered to the surface of the glove mold to be gelled, dried and vulcanized. Gloves can be made.
  • the glove mold is washed with a cleaning solution to remove dirt and dried.
  • a cleaning solution such as nitric acid, an alkaline aqueous solution such as sodium hydroxide or sodium hypochlorite, warm water or the like can be used.
  • the glove mold is immersed in the coagulant solution.
  • the coagulant solution an aqueous solution containing the above-mentioned coagulant in an amount of 5 to 50% by mass, more preferably 10 to 25% by mass can be used.
  • the coagulant solution is preferably heated.
  • the temperature of the coagulant solution is more preferably 30 to 70 ° C, and further preferably 55 to 65 ° C.
  • the drying temperature can usually be from room temperature to 80 ° C., more preferably 55 to 65 ° C.
  • the glove mold may be entirely dried or partially dried.
  • the glove mold to which the coagulant is attached and dried is immersed in the magnetic particle-containing rubber latex according to the present embodiment.
  • magnetic particles are attached to the glove-shaped surface together with rubber.
  • the magnetic particle-containing rubber latex is preferably sufficiently stirred and uniform.
  • the magnetic particle-containing rubber latex may be heated. The heating temperature is preferably 20 to 50 ° C, more preferably 25 to 40 ° C.
  • the glove-type dipping in the magnetic particle-containing rubber latex may be performed once, but can be performed twice or more.
  • the glove mold is dried. Drying can be performed by housing a glove mold in a drying furnace.
  • the drying temperature is preferably 80 to 150 ° C.
  • the drug is separated from the glove mold treated in (e) above (leaching process).
  • a separation method there is a method in which a glove mold to which a magnetic particle-containing rubber latex is attached is treated in a leaching tank containing water.
  • the water is preferably heated.
  • the heating temperature is preferably 30 to 80 ° C., more preferably 40 to 60 ° C.
  • the rubber latex containing magnetic particles adhering to the glove mold is vulcanized.
  • Vulcanization can be performed by heating the glove mold.
  • the heating temperature is preferably 100 ° C. to 150 ° C.
  • the heating temperature is usually 1 minute to 1 hour, preferably 15 to 30 minutes.
  • rubber gloves can be removed from the glove mold to obtain gloves. Further, before removing the gloves from the glove mold, the surface of the gloves can be optionally chlorinated, neutralized with alkali, washed with water and dried.
  • the chlorine treatment is preferably performed at a chlorine concentration of 800 to 2000 ppm.
  • the dipping step (d) includes a step of sequentially immersing a glove mold in a plurality of emulsions having different compositions, and attaching a plurality of layers having different compositions to the glove mold, and at least one of the plurality of emulsions, It can be set as the above-mentioned magnetic particle containing emulsion.
  • a film of a glove can be formed by a plurality of layers having different compositions, and functionality can be enhanced.
  • a plurality of emulsions having different blending ratios of magnetic particles in the magnetic particle-containing emulsion can be prepared, and the glove mold can be sequentially immersed in these magnetic particle-containing emulsions.
  • a magnetic particle-containing emulsion and an emulsion not containing magnetic particles can be prepared, and a glove mold can be sequentially immersed in these emulsions.
  • the glove mold may be immersed once in each emulsion, or the glove mold may be immersed multiple times in the same emulsion. Further, the immersion order is not limited.
  • an emulsion containing no magnetic particles or a magnetic particle-containing emulsion having a low concentration of magnetic particles is attached to the glove mold, and then a magnetic particle-containing emulsion containing magnetic particles or containing a magnetic particle having a high concentration of magnetic particles.
  • a layer not containing magnetic particles or a layer having a low concentration of magnetic particles is formed on the surface of the glove after manufacturing the glove, so that the color of the surface of the glove can be adjusted.
  • the glove according to the present embodiment may be a glove reinforced with a fiber or the like in addition to a glove having a single layer structure by a film formed of rubber or resin.
  • a glove in which a fiber knitted glove and a film formed of rubber or resin are integrated may be used.
  • the gloves according to the present embodiment include a glove that covers the entire palm, a glove that covers from the hand to the elbow and arm, and a glove that covers only the fingertip such as a finger cover.
  • Example 1 In Table 1, the raw material composition and evaluation result of the glove of an Example are shown.
  • TiO 2 TiO 2 white pigment powder, manufactured by Revertex Sdn Bhd.
  • Pigment CI Pigment Blue 15: 3 (phthalocyanine copper) and CI Pigment Violet 23 (8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo [3,2-b: 3 ′, 2′-m ] With triphenodioxazine).
  • Magnetite particles magnetite FeFe 2 O 4 particles, “MAGNETAITE-MA” manufactured by Toda Kogyo Co., Ltd.
  • SDBS Na dodecylbenzenesulfonate, manufactured by KC CHEMICALS (M) SDN BHD.
  • NBR latex “Production of NBR latex” Among the raw material compositions shown in Table 1, according to the composition ratio of the latex, NBR latex (shown as solid content in Table 1), sulfur, SDBS (Na dodecylbenzenesulfonate), vulcanization accelerator, and ZnO are mixed, NBR latex was prepared. During mixing, purified water, aqueous ammonia, and aqueous potassium hydroxide were added to adjust pH. The obtained NBR latex had a solid content of 30% by mass.
  • NBR latex solid content 43.5% by mass, Nantex Industry Co. , Ltd. “Nantex 6720”.
  • Sulfur Made by Tearco Chemical (M) Sdn Bhd.
  • Vulcanization accelerator ZMBT (bis (mercaptobenzothiazole) zinc), manufactured by Tearco Chemical (M) Sdn Bhd.
  • ZnO made by Tearco Chemical (M) Sdn Bhd.
  • the thickness of the obtained glove was 0.089 mm.
  • the results are also shown in Table 1.
  • Measurement of the volume ratio of particles having a particle diameter of secondary particles exceeding 1 ⁇ m was performed by the following method. First, the cross-section of the glove was observed using a scanning electron microscope (SEM) so that 200 to 700 secondary particles were included in a predetermined range, and the diameters of these 200 to 700 secondary particles were determined. It was measured. The secondary particle diameter was measured by measuring the major axis and minor axis of each secondary particle, calculating the diameter of a true sphere having the same volume as each secondary particle, and using this diameter as the secondary particle diameter.
  • the secondary particles were observed as one particle, that is, an aggregate observed by overlapping two or more primary particles.
  • the volume ratio of the particles having a particle diameter of the secondary particles exceeding 1 ⁇ m was obtained as the ratio of the volume of the secondary particles exceeding 1 ⁇ m to the total volume of 200 to 700 secondary particles.
  • secondary particles exceeding 1 ⁇ m were not observed.
  • the average particle size of the primary particles was determined by measuring 200 to 700 primary particle sizes in the same manner as the measurement of the secondary particle size described above and averaging these on a number basis. In the observation with a scanning electron microscope (SEM), the primary particles are observed as one particle. The primary particle size of the raw material magnetite particles was equal to the primary particle size observed in the gloves.
  • Examples 2 to 5 gloves were produced in the same manner as in Example 1 except that the composition ratio of the magnetic particle dispersion was changed as shown in Table 1.
  • Comparative Example 3 “MPF Sacramen (trade name)” manufactured by Aram Co., Ltd. was prepared as a commercially available glove.
  • This glove is a polyethylene resin glove containing 18 to 22% by mass of magnetite (FeFe 2 O 4 ).
  • Table 2 shows an average value of 20% by mass of the amount of magnetite, which is a magnetic particle, as a reference.
  • Example 6 gloves were produced in the same manner as in Example 1 except that the following magnetic particles were used as magnetic particles at 4.8% by mass.
  • Example 6 ⁇ -Fe 2 O 3 ferrite powder, manufactured by Kanto Chemical Co., Inc.
  • Example 7 Manganese / zinc ferrite (Mn / ZnFe 2 O 4 ) powder, manufactured by JFE Chemical Co., Ltd.
  • Example 8 Nickel / zinc ferrite (Ni / ZnFe 2 O 4 ) powder, manufactured by JFE Chemical Co., Ltd.
  • Tables 4 to 6 show the raw material composition and evaluation results of the gloves of the examples.
  • Example 9 to 13 a glove was produced in the same manner as in Example 1 above, except that when the glove mold was immersed in the rubber latex, the glove mold was immersed once in a latex tank having a different composition. .
  • the first latex tank contains a latex containing pigment and no magnetic particles
  • the second latex tank contains 19.5 to 70.0% by mass of magnetic particles. Contains latex without pigments.
  • the first and last rubber latex tanks contain rubber latex containing pigments and no magnetic particles
  • the other rubber latex tanks after the second time contain 38 magnetic particles. It contains rubber latex containing 0 to 70.0% by mass and containing no pigment.
  • the glove mold was immersed once in each rubber latex tank.
  • a layer containing pigment and no magnetic particles is formed on the outer surface of the glove, and a layer containing magnetic particles and no pigment is formed inside the glove, A laminated glove was produced.
  • “Saturation magnetic flux density” The saturation magnetic flux density of the glove was measured under the following conditions using a sample vibrating magnetometer (“VSM-5-15 type” manufactured by Toei Kogyo Co., Ltd.). Magnetization calibration: Ni (nickel), Gd 2 O 3 (gadolinium oxide). Measurement magnetic field: 10 kOe. Measurement temperature: normal temperature.
  • Minimum detection volume Measurement was performed using “MS-3137” manufactured by Nissin Electronics Co., Ltd. as a metal detector.
  • the set detection sensitivity of this metal detector is an Fe sphere of ⁇ 0.5 mm.
  • a glove piece of each size was cut out, and each glove piece was passed through a metal detector to check the presence or absence of detection.
  • the minimum size of the glove piece detected by the metal detector was defined as the minimum detection volume.
  • tensile strength, elongation at break, 100% modulus As the mechanical strength of the glove, tensile strength (MPa), elongation at break (%), and 100% modulus (MPa) were measured according to JIS K6251-1993. Using “STA-1225” manufactured by Orientec Co., Ltd. as a tensile tester, measurement was performed with a dumbbell shape No. 5 and a tensile speed of 500 mm / min.
  • the minimum detection volume by the metal detector is 36 mm 3 or less
  • the saturation magnetic flux density is 4 Gauss or more
  • a smaller glove piece can be detected by the metal detector.
  • a thin glove having excellent mechanical properties and a thickness of 0.091 mm or less could be produced.
  • Comparative Example 1 the amount of magnetic particles was insufficient, the saturation magnetic flux density was 0.1 Gauss or less, and the glove pieces could not be detected by the metal detector.
  • Comparative Example 2 the blending amount of the magnetic particles was excessive, it was difficult to uniformly mix the latex and the magnetic particle dispersion, and color unevenness occurred in the obtained glove.
  • Example 5 Although the minimum detection volume by a metal detector is small, it is thought that there are many compounding quantities of a magnetic particle and elongation rate falls.
  • the magnetic particles are 20% by mass and the minimum detection volume is 0.9 mm 3 .
  • the magnetic particles are 15.0% by mass and the minimum detection volume is 0.7 mm 3 .
  • the minimum detection volume could be reduced with fewer magnetic particles.
  • the secondary particles of the magnetic particles of Example 5 are aggregated, whereas the aggregated state of the secondary particles is not remarkable in the magnetic particles of Comparative Example 3 as shown in FIG. Rather, the primary particles were observed to be uniformly dispersed. That is, in Comparative Example 3, secondary particles exceeding 1 ⁇ m were not observed. It is considered that the minimum detection volume can be reduced in Examples 1 to 5 due to the difference in the aggregation state.
  • Example 6 although the types of magnetic particles were different, all of them were good results as in Example 3 in which the blending amount of the magnetic particles was the same.
  • Example 9 when the glove mold was dipped in latex, the glove mold was dipped multiple times in latex having different compositions.
  • Example 9 as shown in FIG. 3, the cross-sectional structure of the glove was a two-layer structure, but the amount of magnetic particles as a whole film of the glove was almost the same as Example 4. In this case, the minimum detection volume by the metal detector showed almost the same sensitivity as in Examples 4 and 5, respectively, and was a good result.
  • the concentration of magnetic particles in the latex containing magnetic particles was as high as 30% by mass or more, no uneven color was observed on the glove surface, and various physical properties were also good. Met.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Gloves (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Investigating Or Analyzing Materials By The Use Of Magnetic Means (AREA)
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JP2015522848A JP6546086B2 (ja) 2013-06-14 2014-06-12 手袋及びその製造方法
AU2014279085A AU2014279085B2 (en) 2013-06-14 2014-06-12 Glove and production process therefor
US14/898,412 US9808039B2 (en) 2013-06-14 2014-06-12 Glove and production process thereof
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CN106519327A (zh) * 2016-11-18 2017-03-22 淮北智淮科技有限公司 一种手指灵活度锻炼装置及其生产工艺
WO2017065599A1 (en) * 2015-10-15 2017-04-20 Universiti Malaya Glove
CN106617401A (zh) * 2017-01-06 2017-05-10 广州市聚吉科绿色化学共性技术研究院有限公司 一种聚氯乙烯/丁腈复合橡胶手套及其制备方法
CN106617402A (zh) * 2017-01-06 2017-05-10 广州市聚吉科绿色化学共性技术研究院有限公司 一种氟醚/氟硅复合橡胶手套及其制备方法
CN106666878A (zh) * 2017-01-06 2017-05-17 广州市聚吉科绿色化学共性技术研究院有限公司 一种复合橡胶手套及其制备方法
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JP2017193790A (ja) * 2016-04-19 2017-10-26 株式会社東和コーポレーション 手袋および手袋の製造方法
JP2018120921A (ja) * 2017-01-24 2018-08-02 パウダーテック株式会社 フェライト粉、樹脂組成物および成形体
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JP2020019828A (ja) * 2018-07-30 2020-02-06 建設ゴム株式会社 成形品および成形品群
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WO2017026076A1 (ja) * 2015-08-07 2017-02-16 原田産業株式会社 食品用手袋
JP7018888B2 (ja) 2015-10-15 2022-02-14 ウニベルシティ・マラヤ 手袋
WO2017065599A1 (en) * 2015-10-15 2017-04-20 Universiti Malaya Glove
JP2018538462A (ja) * 2015-10-15 2018-12-27 ウニベルシティ・マラヤＵｎｉｖｅｒｓｉｔｉ Ｍａｌａｙａ 手袋
WO2017170426A1 (ja) * 2016-03-31 2017-10-05 パウダーテック株式会社 フェライト粉、樹脂組成物および成形体
JP2017193790A (ja) * 2016-04-19 2017-10-26 株式会社東和コーポレーション 手袋および手袋の製造方法
CN106519327A (zh) * 2016-11-18 2017-03-22 淮北智淮科技有限公司 一种手指灵活度锻炼装置及其生产工艺
CN106617401A (zh) * 2017-01-06 2017-05-10 广州市聚吉科绿色化学共性技术研究院有限公司 一种聚氯乙烯/丁腈复合橡胶手套及其制备方法
CN106617402A (zh) * 2017-01-06 2017-05-10 广州市聚吉科绿色化学共性技术研究院有限公司 一种氟醚/氟硅复合橡胶手套及其制备方法
CN106666878A (zh) * 2017-01-06 2017-05-17 广州市聚吉科绿色化学共性技术研究院有限公司 一种复合橡胶手套及其制备方法
JP2018120921A (ja) * 2017-01-24 2018-08-02 パウダーテック株式会社 フェライト粉、樹脂組成物および成形体
JP2019081886A (ja) * 2017-10-31 2019-05-30 Ａｇｃ株式会社 分散液、フッ素ゴム組成物、フィルム、およびそれらの製造方法
JP7283048B2 (ja) 2017-10-31 2023-05-30 Ａｇｃ株式会社 分散液、フッ素ゴム組成物、フィルム、およびそれらの製造方法
JP2020019828A (ja) * 2018-07-30 2020-02-06 建設ゴム株式会社 成形品および成形品群
JP2022511506A (ja) * 2018-12-07 2022-01-31 スキンプロテクト コーポレイション スンディリアン ブルハド 検出可能かつマルチ検出可能な物品
JP7691364B2 (ja) 2018-12-07 2025-06-11 スキンプロテクト コーポレイション スンディリアン ブルハド 検出可能かつマルチ検出可能な物品

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EP3009021A4 (en) 2017-03-29
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DK3009021T3 (da) 2019-07-01
CN105451584B (zh) 2017-10-31
US20160150840A1 (en) 2016-06-02
EP3009021B1 (en) 2019-03-27
CN105451584A (zh) 2016-03-30
MY186163A (en) 2021-06-30
JP6577614B2 (ja) 2019-09-18

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