EP0997918B1 - Herstellung einer Magnetschicht - Google Patents

Herstellung einer Magnetschicht Download PDF

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Publication number
EP0997918B1
EP0997918B1 EP19990201371 EP99201371A EP0997918B1 EP 0997918 B1 EP0997918 B1 EP 0997918B1 EP 19990201371 EP19990201371 EP 19990201371 EP 99201371 A EP99201371 A EP 99201371A EP 0997918 B1 EP0997918 B1 EP 0997918B1
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Prior art keywords
support
ions
magnetic layer
soft magnetic
process according
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Expired - Lifetime
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EP19990201371
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English (en)
French (fr)
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EP0997918A1 (de
Inventor
Hieronymus Andriessen
Steven Lezy
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Agfa Gevaert NV
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Agfa Gevaert NV
Agfa Gevaert AG
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Priority to EP19990201371 priority Critical patent/EP0997918B1/de
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/0027—Thick magnetic films
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
    • H01F41/16—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates the magnetic material being applied in the form of particles, e.g. by serigraphy, to form thick magnetic films or precursors therefor

Definitions

  • the present invention relates to the preparation of particular types of magnetic layers and to their use in an anti-theft system.
  • H a ferromagnetic sample that is initially demagnetized
  • B a particular flux density
  • the value of H is decreased again the decreasing flux density does not follow the path of increase but decreases at a rate less than that at which it rose.
  • H has reached zero again the value of B is not reduced to zero but to a value called the retentivity or remanence.
  • the sample has retained a permanent magnetization.
  • the value of B may be reduced to zero by reversing the magnetic field to negative and increasing its value to the so-called coercive force or coercivity.
  • H By further increasing H to negative values and then again reversing its direction a hysteresis loop as represented in fig. 1 is completed.
  • a so-called soft ferromagnetic material shows a rather low coercive force ; a so-called semi-soft ferromagnetic material shows a rather high coercive force.
  • This properties are used in a special type of anti-theft labels, e.g. for preventing the theft from clothes out of shops, called EM-EAS labels ( E lectro M agnetic E lectronic A rticle S urveillance). The principle works as follows.
  • a label carrier is covered on one side with a soft magnetic layer having a coercive force of about 39.8 A / m (0.5 Oe), and on the other side with a semi-soft magnetic layer having a coercive force of about 7958 A / m (100 Oe).
  • the detection zone consists of a transmitter which transmits an alternating magnetic field with a force Z M positioned between 0.5 and 100 Oe, and of a receiver.
  • the semi-soft magnetic layer consists of a nickel mesh
  • the soft magnetic layer consists of a complex alloy of Ni a Fe b Co c (Mo) d B e .
  • the problem with these magnetic layers is the fact that they are nowadays applied by means of sputtering in vacuo, a cumbersome and expensive technique.
  • aqueous solution of nickel(II) ions is prepared.
  • a most suitable salt is Ni(NO 3 ) 2 .6H 2 O.
  • the solution is acidified with a small amount of nitric acid.
  • the nickel ions in the solution are reduced to highly dispersed metallic nickel particles of nanosize by means of the addition of a reducing agent.
  • a preferred reducing agent is KBH 4 .
  • the reducing agent can be added to the original nickel salt solution as a solid powder. More preferably, the reducing agent may be dissolved separately in a second aqueous medium and added to the nickel salt solution according to a single jet or a double jet procedure. Preferably, according to the double jet principle, the aqueous medium containing the nickel ions and the second solution containing the reducing agent are added together to a third aqueous medium.
  • the second aqueous solution comprising the reducing agent preferably also contains sulphite ions which strongly enhance the chemical stability of this solution.
  • a protective binder is preferably added to one or more of the three aqueous solutions involved.
  • this protective binder is added to the third aqueous medium wherein both others are jetted.
  • a particularly preferred protective binder is carboxymethylcellulose (CMC).
  • CMC carboxymethylcellulose
  • Other possible binders include gelatin, arabic gum, poly(acrylic acid), cellulose derivatives and other polysaccharides.
  • a complexing agent is present in one of the three aqueous media described above.
  • a preferred complexant is simply the well-known ethylenediaminetetraacetic acid (EDTA) or a homologous compound or a salt thereof.
  • EDTA ethylenediaminetetraacetic acid
  • Another preferred one is citrate, e.g. triammonium citrate.
  • Suitable complexants include diethylenetriamine-pentaacetic acid (DTPA), trans-1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid (CDTA), ethyleneglycol-O,O'-bis(2-aminoethyl)-N,N,N',N'-tetraacetic acid (EGTA), N-(2-hydroxyethyl)ethylenediamine-N,N,N'-triacetic acid (HEDTA), etc.
  • the complexing agent is preferably present in the third aqueous medium to which the other solutions are added according to the double jet principle.
  • the superfluous salts are first removed from the aqueous medium by a washing process, preferably involving ultrafiltration and/or diafiltration. Additionally or alternatively centrifugation can be used.
  • a so-called dispersing aid can be present.
  • this compound is added to the diafiltration liquid at the last stage of the preparation.
  • Suitable dispersing aids in the case of nickel are phosphates, more particularly a hexametaphosphate such as sodium hexametaphosphate.
  • the hexametaphosphate adsorbs to the surface of the alloy particles so that they become negatively charged. By electrostatic repulsion they are kept in dispersion.
  • the phosphate inhibits further oxidation of the surface of the formed nanoparticles.
  • the thin nickel oxide shell that will be formed inevitably around the nanoparticles since the reducing medium disappears during the washing step will be passivated by the hexametaphosphate.
  • the nickel particles are ultrafiltrated e.g. through a Fresenius F60 cartridge and subsequently diafiltrated against a solution of sodium hexametaphosphate in water/ethanol (98.5/1.5).
  • the hexametaphosphate is also preferably added to the third aqueous solution.
  • the obtained final colloidal composition is coated on the substrate by means of a conventional coating technique, such as slide hopper, curtain coating and air-knife coating.
  • a conventional coating technique such as slide hopper, curtain coating and air-knife coating.
  • Suitable coating agents include non-ionic agents such as saponins, alkylene oxides e.g. polyethylene glycol, polyethylene glycol/polypropylen glycol condensation products, polyethylene glycol alkyl esters or polyethylene glycol alkylaryl esters, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or alkylamides, silicone-polyethylene oxide adducts, glycidol derivaties, fatty acid esters of polyhydric alcohols and alkyl esters of saccharides; anionic agenst comprising an acid group such as a carboxy, sulpho, phospho, sulphuric or phosphoric ester group; ampholytic agents such as aminoacids, aminoalkyl sulphonic acids, aminoalkyl sulphates or phosphates, alkyl betaines, and amine-N-oxides; and cationic agents such as aklylamine salt
  • Useful transparent organic resin supports include e.g. cellulose nitrate film, cellulose acetate film, polyvinylacetal film, polystyrene film, polyethylene terephthalate film, polycarbonate film, polyvinylchloride film or poly- ⁇ -olefin films such as polyethylene or polypropylene film.
  • the thickness of such organic resin film is preferably comprised between 0.05 and 0.35 mm.
  • the support is a polyethylene terephthalate layer provided,with a subbing layer. This subbing layer can be applied before or after stretching of the polyester film support.
  • the polyester film support is preferably biaxially stretched at an elevated temperature of e.g.
  • the stretching may be accomplished in two stages, transversal and longitudinal in either order or simultaneously.
  • the subbing layer when present, is preferably applied by aqueous coating between the longitudinal and transversal stretch, in a thickness of 0.1 to 5 mm.
  • the subbing layer preferably contains, as described in EP 0 464 906, a homopolymer or copolymer of a monomer comprising covalently bound chlorine. Examples of said homopolymers or copolymers suitable for use in the subbing layer are e.g.
  • polyvinyl chloride polyvinylidene chloride; a copolymer of vinylidene chloride, an acrylic ester and itaconic acid; a copolymer of vinyl chloride and vinylidene chloride; a copolymer of vinyl chloride and vinyl acetate; a copolymer of butylacrylate, vinyl acetate and vinyl chloride or vinylidene chloride; a copolymer of vinyl chloride, vinylidene chloride and itaconic acid; a copolymer of vinyl chloride, vinyl acetate and vinyl alcohol, etc.
  • Polymers that are water dispersable are preferred since they allow aqueous coating of the subbing layer which is ecologically advantageous.
  • the support may be opaque, such as a paper support, e.g. a plain paper support or a polyolefin coated paper. Furtheron glass, e.g. thin glass packed on roll can be used.
  • the coated substantially pure nickel layer is ferromagnetic of the so-called semi-soft type.
  • the nickel ions are not the sole ion type undergoing reduction but they are mixed with one or more other types of ions.
  • Preferred types of salts for admixture with the nickel salt are iron salts, cobalt salts or molybdene salts, or mixtures of those.
  • soft magnetic layers By choosing the appropriate type(s) of ions and the appropriate admixture ratio(s) so-called soft magnetic layers can be prepared.
  • a support preferably a paper support
  • a semi-soft . magnetic layer based on substantially pure nickel prepared according to the present invention, and on the opposite side with a soft magnetic layer based on an admixture of nickel particles with other metal particles prepared according to the present invention.
  • the resulting labels can be used in a EM-EAS system ( E lectro M agnetic E lectronic A rticle S urveillance). Furtheron, such a label can also be produced when a semi-soft magnetic layer prepared according to the present invention is applied to a commercially available soft magnetic layer on a support.
  • PERMALLOY (trade mark of Western Electric), METGLAS (trade mark of Allied Signal Co.), and ATALANTE (trade mark of IST/Bekaert).
  • Particularly useful METGLAS products are type 2705M, consisting of Co 69 Fe 4 Ni 1 B 12 Si 12 , and type 2826MB, consisting of Fe 40 Ni 38 Mo 4 B 12 .
  • such a label can also be produced when a soft magnetic layer prepared according to the present invention is applied to a commercially available semi-soft magnetic layer on a support.
  • Examples of such commercial products are VICALLOY (trade mark of Telecon Metals Ltd.), AMOKROME (trade mark of Arnold Engineering), and CROVAK (trade mark of Vacuumschmelze GmbH).
  • the Ni-Fe-dispersion was prepared as follows:
  • solution 1 at a flow rate of 12.4 ml/min was simultaneously added with solution 2 at 12.4 ml /min.
  • the NiFe dispersion was ultrafiltrated through a Fresenius F60 cartridge and diafiltrated with a 0.36 % solution of sodium hexametaphosphate in water/ethanol (98.5/1.5).
  • the dispersion was stirred and 10 ml of a 12.5% solution of Saponine Quillaya (Schmittmann) in water/ethanol (80/20) was added. This is the Ni-Fe dispersion.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Soft Magnetic Materials (AREA)

Claims (13)

  1. Ein durch die nachstehenden Schritte gekennzeichnetes Verfahren zur Herstellung eines magnetischen Elements mit einem Träger und zumindest einer magnetischen Schicht :
    (1) Ansetzen einer wässrigen Lösung, die einen oder mehrere Typen von Metallionen, wozu Nickel(II)-Ionen zählen, enthält,
    (2) chemisches Reduzieren der einen oder mehreren Metallionen mittels eines Reduktionsmittels, wobei eine wässrige Dispersion von Metallteilchen, wozu Nickel zählt, gebildet wird,
    (3) Entfernen aller überflüssigen Ionen aus der wässrigen Dispersion durch einen Waschschritt oder durch Zentrifugation,
    (4) Auftrag der so erhaltenen wässrigen Dispersion auf einen Träger.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Reduktionsmittel mittels einer separaten zweiten wässrigen Lösung zugesetzt wird.
  3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass die separate zweite wässrige Lösung ferner Sulfitionen enthält.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Reduktionsmittel KBH4 ist.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der Waschschritt einen Ultrafiltrationsschritt und/oder einen Diafiltrationsschritt umfasst.
  6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, dass während des Ultrafiltrationsschritts und/oder Diafiltrationsschritts als Dispersionsmittel ein Phosphat verwendet wird.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass das Phosphat ein Hexametaphosphat ist.
  8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Metallionen im Wesentlichen nur Nickel(II)-Ionen sind, wodurch nach den Schritten (1) bis (4) eine halbweiche magnetische Schicht erhalten wird.
  9. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Metallionen außer Nickelionen ferner Eisenionen, Kobaltionen, Molybdänionen oder Gemische derselben umfassen, wodurch nach den Schritten (1) bis (4) eine weichmagnetische Schicht erhalten wird.
  10. Magnetisches Element mit einem Träger und an einer Seite des Trägers einer nach dem Verfahren von Anspruch 8 hergestellten halbweichen magnetischen Schicht und an der anderen Seite des Trägers einer weichmagnetischen Schicht.
  11. Magnetisches Element mit einem Träger und an einer Seite des Trägers einer halbweichen magnetischen Schicht und an der anderen Seite des Trägers einer nach dem Verfahren von Anspruch 9 hergestellten weichmagnetischen Schicht.
  12. Magnetisches Element mit einem Träger und an einer Seite des Trägers einer nach dem Verfahren von Anspruch 8 hergestellten halbweichen magnetischen Schicht und an der anderen Seite des Trägers einer nach dem Verfahren von Anspruch 9 hergestellten weichmagnetischen Schicht.
  13. Verwendung eines magnetischen Elements nach einem der Ansprüche 10 bis 12 als Etikett in einem EM-EAS-System (Elektromagnetische Elektronische Artikelsicherung)
EP19990201371 1998-10-26 1999-04-29 Herstellung einer Magnetschicht Expired - Lifetime EP0997918B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19990201371 EP0997918B1 (de) 1998-10-26 1999-04-29 Herstellung einer Magnetschicht

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP98203868 1998-10-26
EP98203868 1998-10-26
EP19990201371 EP0997918B1 (de) 1998-10-26 1999-04-29 Herstellung einer Magnetschicht

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EP0997918A1 EP0997918A1 (de) 2000-05-03
EP0997918B1 true EP0997918B1 (de) 2004-07-14

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Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5767156A (en) * 1980-10-13 1982-04-23 Nec Corp Electroless plating bath
JPH0229753B2 (ja) * 1981-06-29 1990-07-02 Nippon Electric Co Mudenkaimetsukihoho
JPH02108221A (ja) * 1988-10-18 1990-04-20 Mitsubishi Kasei Corp 磁気記録媒体
JPH09232142A (ja) * 1996-02-28 1997-09-05 Unitika Ltd 磁気素子及びその製造方法

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