EP0085414B1 - Marking means, method of manufacture and their use in marking explosives - Google Patents

Marking means, method of manufacture and their use in marking explosives Download PDF

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Publication number
EP0085414B1
EP0085414B1 EP83100815A EP83100815A EP0085414B1 EP 0085414 B1 EP0085414 B1 EP 0085414B1 EP 83100815 A EP83100815 A EP 83100815A EP 83100815 A EP83100815 A EP 83100815A EP 0085414 B1 EP0085414 B1 EP 0085414B1
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EP
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Prior art keywords
weight
amounts
oxides
salts
pigments
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EP83100815A
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German (de)
French (fr)
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EP0085414A1 (en
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Wolfgang Weller
Rudolf Dr. Eggimann
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Coathylene SA
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Coathylene SA
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Priority to AT83100815T priority Critical patent/ATE18818T1/en
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/008—Tagging additives
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps

Definitions

  • the present invention relates to marking agents, in particular for marking explosives, which allow the substance used to be identified with respect to its origin and composition and, if appropriate, also the date of manufacture using microanalytical methods.
  • the invention further relates to the method for producing such marking agents and their use, in particular for marking explosives.
  • the increasing theft and unauthorized use of explosives has led to the need to be able to clearly prove the origin, type and possibly also the time of manufacture of explosives. This need has already been reflected in legal provisions; see. Ordinance on Explosive Substances of March 26, 1980 of the Swiss Federal Council, Art. 5, Sentence 3, which reads: «The explosives must contain a marking substance which can be used to reliably determine its origin even after the explosion.
  • the labeling substance requires the approval of the central office, which has to take account of changed circumstances.
  • the 3 M product described above partially fulfills these requirements, but increases the costs of the explosive to a not inconsiderable extent due to its complicated manufacturing process.
  • the object of the invention is to provide a marking agent which fulfills all of the above requirements for a marking agent for explosives.
  • the iron powder and / or powder of ferromagnetic alloys must be present at least in quantities of 1% so that the marking agent can be removed from the explosion debris with the help of magnets. In general, amounts of 3 to 20% by weight of ferromagnetic material are used. Quantities of 5 to 12% by weight have proven particularly useful.
  • the fluorescent pigments are said to be insoluble in water and organic solvents, while the fluorescent substances are said to be water-insoluble but soluble in organic solvents. This makes it easy to separate these groups of substances from one another and to determine them independently of one another.
  • the color pigments, oxides and / or salts of rare metals and oxides and / or sparingly soluble salts of rare earths should also be insoluble in water and organic solvents, so that they remain in the residue in any case and can then be clearly determined analytically next to one another.
  • Such granules can be used without Difficulty in grinding powders with a grain size of 100 to 1 200! Jm. It is desirable to obtain relatively narrow particle size distributions because particles of the same size behave more uniformly under the conditions of the explosion than products with a very wide particle size distribution. If the edge lengths of the granules are greater than 6 mm, marking agents with a relatively broad particle size distribution are obtained during grinding, which is particularly undesirable when marking explosives. In the case of explosives, optimum results have been achieved with marking agents, which are in the range from 200 to 600 ⁇ m, given the most uniform particle sizes possible. If desired, the particles of particularly large and particularly small edge lengths can be separated from the ground product by sieving, thereby achieving a narrow grain size distribution. Furthermore, the optimal grain size distribution can also depend somewhat on the type of explosive to be marked, since the marking means should also be mixed with the respective explosive as homogeneously as possible.
  • Polyethylenes, polypropylenes, polyamides, polycarbonates, polyesters, polyoximethylenes and acrylonitrile-butadiene-styrene copolymers have proven particularly useful as plastics of high molecular weight, thermoplastically processable polymers with low water absorption, high specific heat, low thermal conductivity and low specific weight.
  • These polymers can be homogeneously mixed with the analytically detectable groups of substances in the molten state without decomposition. They are also suitable for keeping these substances unchanged over a long period of time and for their analytical determination for the purpose of decoding. Since the polymers used have reproducible thermal properties that can be determined microanalytically using differential thermal analysis, these criteria can also be used for identification and decoding.
  • the molecular weight or the melt viscosity of the polymers are not critical as long as the polymers can be processed thermoplastically well, but are sufficiently stable against water and organic solvents at room temperature.
  • the high specific heat and low thermal conductivity protect the substances introduced into the plastic from the effects of the explosion heat.
  • the low specific weight makes it easier to separate the marking agents according to the invention from the explosion debris by means of liquids of a suitable specific density.
  • the ferromagnetic parts only serve to separate and enrich the marking agents according to the invention from the explosion debris and not for analytical decoding.
  • Iron powders with an upper grain size of less than 60 .mu.m have proven particularly useful as ferromagnetic materials. Such iron powder with a purity content of 99.5% is available, for example, under the name RZ 60 from Mannesmann-DEMAG.
  • RZ 60 from Mannesmann-DEMAG.
  • all other ferromagnetic alloys can also be used, provided they are available in powder form. If these alloys contain relatively rare alloy components, these can in principle also be used for identification and decoding.
  • the substances added to the marking agents according to the invention should be resistant to brief heat effects of 200 to 300 ° C.
  • all those pigments that can be clearly distinguished from one another by their fluorescence spectrum and their own color are suitable as fluorescent pigments.
  • suitable fluorescent pigments are the pigments sold by Industrial Colors Ltd., England, under the name FLARE 910, orange, green and yellow, or the LUMILUX C luminous pigments from Riedel-de Haen AG, FRG.
  • all fluorescent substances which are soluble in organic solvents and which can be removed from the marking agents with the aid of organic solvents are suitable as fluorescent substances.
  • the fluorescent substances should preferably be water-insoluble so that they cannot already be dissolved out of the marking agent by water.
  • Suitable fluorescent substances are the products sold under the names UVITEX OB, UVITEX 127 and UVITEX OB-P from the company Ciba and under the names FLUOLITE XNR and FLUOLITE XMP from the company ICI. All sufficiently insoluble and heat-stable pigments whose emission spectrum can be clearly identified can in turn be used as color pigments.
  • Suitable dye pigments are e.g. B. Sicoplast yellow 12-0190 and Sicoplast red 32-0300 and z. B. the pigments sold by ICI under the name Waxoline with the colors blue, ruby red, green and yellow.
  • titanium dioxide, copper oxide, zinc oxide, strontium carbonate, cadmium sulfide, antimony trioxide, barium sulfate, lanthanum trioxide and bismuth trioxide are suitable as sparingly soluble and heat-stable oxides and / or salts of rare metals.
  • Particularly suitable oxides and / or sparingly soluble salts of the rare earths are cerium IV oxide and the other oxides and possibly oxalates of the lantanides. Otherwise, poorly soluble and heat-stable oxides and / or salts of all metals, alone or in combination, can be used, provided that they are microanalytically unique, e.g. B. by X-ray fluorescence spectrometry can be identified.
  • the marking agents according to the invention are in principle suitable for marking substances with regard to their origin, their composition and their date of manufacture, provided there is serious interest in this. In principle, such interest exists or arises in substances that can affect the safety of the population.
  • the marking means according to the invention can be used in particular for the identification of powdery goods in which it is sensible or important for security reasons or criminological reasons to be able to identify them in terms of type, manufacturer and date of manufacture. This problem is of particular importance already with explosives.
  • the marking agents according to the invention should therefore be used in particular for marking explosives.
  • the finished marking agent has a grain size distribution of 80 to 630 ⁇ m with a weight average of 310 ⁇ m.
  • the following commercially available materials were used as raw materials:
  • ELTEX is a trademark of Solvay, Belgium.
  • RZ 60 with an upper grain size of 60 ⁇ m and a purity of 99.5%.
  • RZ 60 is a trademark of Mannesmann-DEMAG, B.R.D.
  • TIMONOX-WHITE STAR with a purity of 99%.
  • TIMONOX-WHITE STAR is a trademark of ASSOCIATED LEAD Manufacturers Ltd., England.
  • the cylindrical granules thus obtained with an edge length of 3 mm are ground according to Example 1 to a final fineness of 80-630 ⁇ m.
  • Coathylene HO 2454 based on Lotrene MD 0707 with a grain size distribution of 80-630 ⁇ .m, a melt index (2.16 Kp / 190 ° C) of 7 g / 10 min. and a density (23 ° C) of 0.924 g / cm 3 .
  • Coathylene is a trademark of Plast-Labor SA, Switzerland, Lotrene is a trademark of CdF, France.
  • Kronos is a brand name of Kronos-Titan GmbH, FRG.
  • Example 1 melting temperature in the extruder is 195 ° C
  • dry, powdery components are used to produce cylindrical granules with an edge length of 5 mm and, according to the process from Example 1, ground to a final fineness of 80-630 ⁇ m:
  • Moplen FL V 20 with a grain size distribution of 40-450 ⁇ m, a melt index (2.16 Kp / 230 ° C) of 16 g / 10 min. and a density (23 ° C) of 0.90 g / cm 3 .
  • Moplen is a trademark of Montedison, Italy.
  • Example 1 The following components were mixed, homogenized, granulated and ground in an analogous manner to that described in Example 1:
  • Uvitex OB without self-coloring, but with blue fluorescence at 435 nm (max. X).
  • Uvitex is a brand name of the company Ciba-Geigy AG, Switzerland.
  • Sicoplast is a trademark of BASF, B.R.D.
  • Marking agents according to Examples 1 to 4 above were mixed with explosives in amounts of 0.05 to 1% by weight.
  • the marking agent was enriched from the debris from test explosions using magnets.
  • the mixture of marking agent and other ferromagnetic debris was separated by aqueous salt solutions of different densities.
  • the fraction containing only the labeling agent was analyzed for its components. It was easily possible to differentiate between the different marking agents and thus to identify the explosives used.

Abstract

1. A tracer (marking agent) containing a) at least 1 per cent by weight of iron powder and/or powder of a ferromagnetic alloy and at least two of the following groups of substances : b) fluorescent pigments ; c) organic solvent-soluble, water-insoluble fluorescent materials ; d) colorant pigments ; e) sparingly soluble and heat-stable oxides and/or salts of rarer metals ; f) oxides and/or sparingly soluble salts of rare-earth metals ; in microanalytically well detectable amounts in the form of a homogeneous mixture with a thermoplastic material, characterized in that the thermoplastically processable material is a high molecular weight synthetic materials having a low water absorption capacity, a high specific heat capacity, a low thermal conductivity, and a low specific gravity, more specifically a synthetic material selected from the group consisting of polyethylenes, polypropylenes, polyamides, polycarbonates, polyesters, polyoxymethylenes and acrylonitrile-butadiene-styrene copolymers.

Description

Gegenstand der vorliegenden Erfindung sind Markierungsmittel, insbesondere zur Markierung von Sprengstoffen, welche eine Identifizierung des verwendeten Stoffes bezüglich Herkunft und Zusammensetzung und ggf. auch Herstellungsdatum mit Hilfe mikroanalytischer Methoden gestatten. Weiterhin betrifft die Erfindung das Verfahren zur Herstellung solcher Markierungsmittel und deren Verwendung insbesondere zur Markierung von Sprengstoffen. Die zunehmende Entwendung und unerlaubte Benutzung von Sprengstoffen hat zu dem Bedürfnis geführt, die Herkunft, die Art und ggf. auch den Herstellungszeitpunkt von Sprengstoffen eindeutig nachweisen zu können. Dieses Bedürfnis hat bereits in gesetzlichen Bestimmungen Niederschlag gefunden ; vgl. Verordnung über explosionsgefährliche Stoffe vom 26.3.1980 des Schweizer Bundesrates, Art. 5, Satz 3, welcher lautet : « Der Sprengstoff muß eine Markierungssubstanz enthalten, über die sich seine Herkunft auch nach der Explosion sicher feststellen läßt. Die Markierungssubstanz bedarf der Genehmigung der Zentralstelle, welche geänderten Verhältnissen Rechnung zu tragen hat.The present invention relates to marking agents, in particular for marking explosives, which allow the substance used to be identified with respect to its origin and composition and, if appropriate, also the date of manufacture using microanalytical methods. The invention further relates to the method for producing such marking agents and their use, in particular for marking explosives. The increasing theft and unauthorized use of explosives has led to the need to be able to clearly prove the origin, type and possibly also the time of manufacture of explosives. This need has already been reflected in legal provisions; see. Ordinance on Explosive Substances of March 26, 1980 of the Swiss Federal Council, Art. 5, Sentence 3, which reads: «The explosives must contain a marking substance which can be used to reliably determine its origin even after the explosion. The labeling substance requires the approval of the central office, which has to take account of changed circumstances.

Bisher ist erst ein derartiges Markierungsmittel auf den Markt gekommen. Es handelt sich um ein Produkt der Firma 3 M, welches aus einem Laminat von 9 Schichten eines Melaminharzes besteht. In die 9 Schichten des Melaminharzes sind verschiedene Stoffe wie Fluoreszenzpigment, Farbstoffe und magnetisches Material eingearbeitet. Es ist anzunehmen, daß zunächst Folien oder Platten hergestellt werden, die anschließend zerbrochen und gemahlen werden. Ein Produkt dieser Art ist beispielsweise in der US-PS 4053433 beschrieben.So far, only such a marking agent has come onto the market. It is a product of the company 3 M, which consists of a laminate of 9 layers of a melamine resin. Various substances such as fluorescent pigment, dyes and magnetic material are incorporated into the 9 layers of the melamine resin. It can be assumed that foils or plates are first produced, which are then broken and ground. A product of this type is described, for example, in US Pat. No. 4,053,433.

Aus den US-PS 3 772 200 sowie der entsprechenden DE-PS 2 343 774 ist bekannt, vier unterschiedliche, meist seltene Elemente, vorwiegend in Form ihrer Oxide zu mischen, in einem Muffelofen in eine Glasmasse einzuschmelzen und aus dieser Gesamtschmelze dann durch übliche Verfahren Mikroglaskugeln herzustellen. Diese Produkte überstehen zwar die Sprengstoffexplosion, können aber nur sehr schwierig wieder aufgefunden und vom Explosionschutt getrennt werden. Eine angebliche Verbesserung dieses Produktes wird in der US-PS 3 897 284 beschrieben, bei welcher anstelle von Glas nicht klebende organische Substanzen mit einem Schmelzpunkt über 60 °C verwendet werden sollen. Die Verbesserung soll insbesondere darin bestehen, daß die so erhaltenen Produkte mit Sprengstoff besser verträglich sind und nicht dazu neigen, deren Empfindlichkeit zu steigern, wie die Glaskügelchen. Als nichtklebende organische Substanzen wurden in den Beispielen ausschließlich extrem niedermolekulare Polyäthylene, Paraffinwachse oder Epoxyharze verwendet, da es nur mit diesen möglich ist, nach der Einbettung der Metalloxide aus dem Gemisch noch ein Pulver, das hergestellt werden muß, zu erhalten. Dies ist in sämtlichen Beispielen durch Sprühtrocknung erfolgt. Sprühtrocknung ist aber nur mit organischen Substanzen möglich, die bei den gegebenen Temperaturen eine extrem niedrige Viskosität besitzen. Die so erhaltenen Produkte waren offensichtlich wiederum für die Praxis nicht brauchbar und führten nicht zu Handelsprodukten.From US Pat. No. 3,772,200 and the corresponding German Pat. No. 2,343,774 it is known to mix four different, mostly rare elements, predominantly in the form of their oxides, in a muffle furnace in a glass mass and then from this total melt by conventional methods To produce micro glass balls. Although these products survive the explosive explosion, it is very difficult to find them again and separate them from the explosion debris. An alleged improvement of this product is described in US Pat. No. 3,897,284, in which non-adhesive organic substances with a melting point above 60 ° C. are to be used instead of glass. The improvement is said to be in particular that the products thus obtained are more compatible with explosives and do not tend to increase their sensitivity, like the glass beads. In the examples, only extremely low molecular weight polyethylenes, paraffin waxes or epoxy resins were used as non-adhesive organic substances, since it is only with these that a powder that has to be produced can be obtained from the mixture after the metal oxides have been embedded. In all examples, this was done by spray drying. Spray drying is only possible with organic substances that have an extremely low viscosity at the given temperatures. The products obtained in this way were obviously in turn unusable in practice and did not lead to commercial products.

Aus den US-PS 4131 064 und US-PS 4197104 sind andere Markierungsmittel bekannt, die mit Hilfe eines Kaliumsilikatbinders zu Partikeln verarbeitet und ggf. noch mit einer dünnen folyäthylene-Schicht ummantelt wurden. Zusätzlich wurde versucht, durch Zusatz verschiedener Ferrite Produkte mit verschiedenen Curie-Punkten zu erhalten. Auch diese Produkte haben offensichtlich einen negativen Einfluß auf Stabilität und Lagerfähigkeit der Sprengstoffe gehabt. Weiterhin scheint sich die Kodierung durch den verschieden großen Einfluß der Temperatur bei der Explosion mehr oder weniger stark verändert zu haben, so daß eine eindeutige Dekodierung nicht mehr möglich ist. Aus den US-PS 3 961 106, 3 967 990 und 3 993 838 ist bekannt, die weiter oben beschriebenen Markierungsmittel mit einer dünnen Schicht von niedermolekularem Polyäthylen oder Wachs zu überziehen, um die Verträglichkeit mit dem Sprengstoff zu erhöhen. Aber auch derartige Produkte sind offensichtlich bisher nicht in der Lage gewesen, alle Anforderungen der Praxis zu erfüllen.From US Pat. No. 4,131,064 and US Pat. No. 4,197,104, other marking agents are known which have been processed into particles with the aid of a potassium silicate binder and, if appropriate, have been coated with a thin layer of foleyethylene. In addition, attempts were made to obtain products with different Curie points by adding different ferrites. These products obviously also had a negative impact on the stability and shelf life of the explosives. Furthermore, the coding seems to have changed to a greater or lesser extent due to the differently large influence of the temperature during the explosion, so that a clear decoding is no longer possible. From US Pat. Nos. 3,961,106, 3,967,990 and 3,993,838 it is known to coat the marking agents described above with a thin layer of low molecular weight polyethylene or wax in order to increase the compatibility with the explosive. However, products of this type have obviously not yet been able to meet all practical requirements.

Ein allen Anforderungen genügendes Markierungsmittel muß folgende Bedingungen erfüllen :

  • a) Das Markierungsmittel muß über Jahre im Sprengstoff unverändert erhalten bleiben. Es darf den Sprengstoff nicht instabilisieren oder seine Zusammensetzung verändern.
  • b) Das Markierungsmittel muß die Explosion überstehen und am Explosionsort verbleiben.
  • c) Das Markierungsmittel muß im übrigen Explosionsschutt auffindbar sein, von diesem abtrennbar und eindeutig analysierbar sein.
  • d) Das Markierungsmittel muß auf einem System mit sehr hoher Variierbarkeit bestehen und dabei Verbindungen enthalten, die zumindest in dieser Kombination in der Umwelt nicht vorkommen.
  • e) Das Markierungsmittel muß im Mikromaßstab gut und eindeutig analysierbar sein.
  • f) Das Markierungsmittel muß gegen Wasser und übliche Lösungsmittel beständig sein.
A marking agent that meets all requirements must meet the following conditions:
  • a) The marking agent must remain unchanged in the explosives for years. It must not instabilize the explosive or change its composition.
  • b) The marking agent must survive the explosion and remain at the explosion site.
  • c) The marking agent must be found in the rest of the explosion debris, separable from it and clearly analyzable.
  • d) The marking agent must insist on a system with a very high variability and contain compounds which, at least in this combination, do not occur in the environment.
  • e) The marking agent must be well and clearly analyzable on a micro scale.
  • f) The marking agent must be resistant to water and common solvents.

Das oben beschriebene Produkt der Firma 3 M erfüllt diese Voraussetzungen zum Teil, erhöht jedoch auf Grund seines komplizierten Herstellungsprozesses die Kosten des Sprengstoffes in nicht unerheblichem Maße.The 3 M product described above partially fulfills these requirements, but increases the costs of the explosive to a not inconsiderable extent due to its complicated manufacturing process.

Die Erfindung hat sich die Aufgabe gestellt, ein Markierungsmittel zur Verfügung zu stellen, welches alle oben genannten Anforderungen an ein Markierungsmittel für Sprengstoffe erfüllt.The object of the invention is to provide a marking agent which fulfills all of the above requirements for a marking agent for explosives.

Es wurde gefunden, daß überraschenderweise hochmolekulare Kunststoffe mit geringer Wasseraufnahmefähigkeit, hoher spezifischer Wärme, geringer Wärmeleitfähigkeit und geringem spezifischem Gewicht, insbesondere aus der Gruppe der Polyäthylene, Polypropylene, Polyamide, Polycarbonate, Polyester, Polyoximethylene oder Acrylnitril-Butadien-Styrolcopolymere geeignet sind, thermoplastisch verarbeitbar zu sein, um

  • a) mindestens 1 Gew.-% Eisenpulver und/oder Pulver ferromagnetischer Legierungen sowie mindenstens 2 der folgenden Substanzgruppen,
  • b) Fluoreszenzpigmente,
  • c) in organischen Lösungsmitteln lösliche, wasserunlösliche Fluoreszenzstoffe,
  • d) Farbpigmente,
  • e) schwer lösliche und hitzebeständige Oxide und/oder Salze von selteneren Metallen,
  • f) Oxide und/oder schwerlösliche Salze seltener Erden in mikroanalytisch gut erfaßbaren Mengen, homogen vermischt aufzunehmen und Markierungsmittel mit hervorragenden Eigenschaften zu bilden. Derartige Kunststoffe mit Inhaltstoffen sind selbstverständlich nicht mehr durch Sprühtrocknung pulverisierbar, sie lassen sich jedoch nach dem Abkühlen der Schmelze granulieren und vermahlen. Die so erhaltenen Produkte erfüllen alle obigen Bedingungen für ein gutes Markierungsmittel. Die Teilchengröße der Markierungsmittel nach dem Vermahlen beträgt vorzugsweise 100 bis 1 200 µm.
It has been found that surprisingly high molecular weight plastics with low water absorption, high specific heat, low thermal conductivity and low specific Weight, in particular from the group of polyethylenes, polypropylenes, polyamides, polycarbonates, polyesters, polyoximethylenes or acrylonitrile-butadiene-styrene copolymers, are suitable for being thermoplastically processable in order to
  • a) at least 1% by weight of iron powder and / or powder of ferromagnetic alloys and at least 2 of the following groups of substances,
  • b) fluorescent pigments,
  • c) water-insoluble fluorescent substances which are soluble in organic solvents,
  • d) color pigments,
  • e) poorly soluble and heat-resistant oxides and / or salts of rare metals,
  • f) to absorb oxides and / or sparingly soluble salts of rare earths in microanalytically easily detectable amounts, homogeneously mixed and to form marking agents with excellent properties. Such plastics with ingredients can of course no longer be pulverized by spray drying, but they can be granulated and ground after the melt has cooled. The products thus obtained meet all of the above conditions for a good marking agent. The particle size of the marking agents after grinding is preferably 100 to 1200 μm.

Erfindungswesentlich ist, daß die verwendeten Kunststoffe hochmolekular und thermoplastisch verarbeitbar sind und gleichzeitig geringe Wasseraufnahmefähigkeit, hohe spezifische Wärme, geringe Wärmeleitfähigkeit und geringes spezifisches Gewicht aufweisen. Das erfindungsgemäße Verfahren zur Herstellung von Markierungsmitteln enthaltend

  • a) mindestens 1 Gew.-% Eisenpulver und/oder Pulver ferromagnetischer Legierungen sowie mindenstens 2 der folgenden Substanzgruppen,
  • b) Fluoreszenzpigmente,
  • c) in organischen Lösungsmitteln lösliche, wasserunlösliche Fluoreszenzstoffe,
  • d) Farbpigmente,
  • e) schwer lösliche und hitzebeständige Oxide und/oder Salze von selteneren Erden,
  • f) Oxide und/oder schwerlösliche Salze seltener Erden in mikroanalytisch gut erfaßbaren Mengen, homogen vermischt in einem thermoplastischen Material, ist dadurch gekennzeichnet, daß man als thermoplastisch verarbeitbares Material einen hochmolekularen Kunststoff mit geringer Wasseraufnahmefähigkeit, hoher spezifischer Wärme, geringer Wärmeleitfähigkeit und geringem spezifischen Gewicht, insbesondere aus der Gruppe der Polyäthylene, Polypropylene, Polyamide, Polycarbonate, Polyester, Polyoximethylene oder Acrylnitril-Butadien-Styrolcopolymere, verwendet, die Substanzen a) bis f) in die Schmelze einbringt, homogen vermischt, das Gemisch granuliert und vermahlt.
It is essential to the invention that the plastics used can be processed in a high molecular weight and thermoplastically and at the same time have low water absorption capacity, high specific heat, low thermal conductivity and low specific weight. Containing the inventive method for the production of marking agents
  • a) at least 1% by weight of iron powder and / or powder of ferromagnetic alloys and at least 2 of the following groups of substances,
  • b) fluorescent pigments,
  • c) water-insoluble fluorescent substances which are soluble in organic solvents,
  • d) color pigments,
  • e) sparingly soluble and heat-resistant oxides and / or salts of rare earths,
  • f) Oxides and / or sparingly soluble salts of rare earths in amounts that are easy to detect in a microanalytical manner, homogeneously mixed in a thermoplastic material, is characterized in that the thermoplastic processable material is a high-molecular plastic with low water absorption, high specific heat, low thermal conductivity and low specific weight , in particular from the group of polyethylenes, polypropylenes, polyamides, polycarbonates, polyesters, polyoximethylenes or acrylonitrile-butadiene-styrene copolymers, is used, which brings substances a) to f) into the melt, homogeneously mixed, the mixture granulated and ground.

Das Eisenpulver und/oder Pulver ferromagnetischer Legierungen muß mindestens in Mengen von 1 % vorliegen, damit das Markierungsmittel mit Hilfe von Magneten aus dem Explosionsschutt herausgeholt werden kann. Im allgemeinen werden Mengen von 3 bis 20 Gew.-% ferromagnetischen Materials eingesetzt. Besonders bewährt haben sich Mengen von 5 bis 12 Gew.-%.The iron powder and / or powder of ferromagnetic alloys must be present at least in quantities of 1% so that the marking agent can be removed from the explosion debris with the help of magnets. In general, amounts of 3 to 20% by weight of ferromagnetic material are used. Quantities of 5 to 12% by weight have proven particularly useful.

Zur eindeutigen Kodierung und Dekodierung der erfindungsgemäßen Markierungsmittel müssen mindestens 2 der Substanzgruppen Fluoreszenzpigmente, Fluoreszenzstoffe, Farbpigmente, Oxide und/oder Salze von selteneren Metallen sowie Oxide und/oder schwerlösliche Salze seltener Erden vorliegen. Je mehr verschiedene Substanzgruppen zum Einsatz kommen, umso größer ist die Variierbarkeit und umso leichter ist eine eindeutige Zuordnung nach Hersteller, Herstellungsdatum und Zusammensetzung des Sprengstoffes möglich. Um die Substanzgruppen in den erfindungsgemäßen Markierungsmitteln auch mikroanalytisch gut erfassen zu können, sollen diese in den folgenden Mengen vorliegen :

  • b) Fluoreszenzpigmente in Mengen von 0,1 bis 8 Gew.-%, vorzugsweise 2 bis 5 Gew.-%,
  • c) Fluoreszenzstoffe in Mengen von 0,1 bis 5 Gew.-%, vorzugsweise 1 bis 3 Gew.-%,
  • d) Farbpigmente in Mengen von 0,5 bis 8 Gew.-%, vorzugsweise 1 bis 5 Gew.-%,
  • e) Oxide und/oder Salze von selteneren Metallen in Mengen von 0,5 bis 8 Gew.-%, vorzugsweise 1 bis 5 Gew.-%,
  • f) Oxide und/oder Salze seltener Erden in Mengen von 0,5 bis 5 Gew.-%, vorzugsweise 1 bis 3 Gew.-%.
For clear coding and decoding of the marking agents according to the invention, at least 2 of the substance groups fluorescent pigments, fluorescent substances, color pigments, oxides and / or salts of rarer metals as well as oxides and / or sparingly soluble salts of rare earths must be present. The more different groups of substances are used, the greater the variability and the easier it is to assign them clearly to the manufacturer, date of manufacture and composition of the explosive. In order to also be able to detect the groups of substances in the marking agents according to the invention in a good microanalytical manner, they should be present in the following amounts:
  • b) fluorescent pigments in amounts of 0.1 to 8% by weight, preferably 2 to 5% by weight,
  • c) fluorescent substances in amounts of 0.1 to 5% by weight, preferably 1 to 3% by weight,
  • d) color pigments in amounts of 0.5 to 8% by weight, preferably 1 to 5% by weight,
  • e) oxides and / or salts of rarer metals in amounts of 0.5 to 8% by weight, preferably 1 to 5% by weight,
  • f) oxides and / or salts of rare earths in amounts of 0.5 to 5% by weight, preferably 1 to 3% by weight.

Die Fluoreszenzpigmente sollen unlölich in Wasser und organischen Lösungsmitteln sein, während die Fluoreszenzstoffe zwar wasserunlöslich, aber in organischen Lösungsmitteln löslich sein sollen. Hierdurch lassen sich diese Substanzgruppen leicht voneinander trennen und unabhängig voneinander analytisch bestimmen. Auch die Farbpigmente, Oxide und/oder Salze von selteneren Metallen und Oxide und/oder schwerlösliche Salze seltener Erden sollen in Wasser und organischen Lösungsmitteln unlöslich sein, so daß sie auf alle Fälle im Rückstand verbleiben und dann nebeneinander eindeutig analytisch bestimmt werden können.The fluorescent pigments are said to be insoluble in water and organic solvents, while the fluorescent substances are said to be water-insoluble but soluble in organic solvents. This makes it easy to separate these groups of substances from one another and to determine them independently of one another. The color pigments, oxides and / or salts of rare metals and oxides and / or sparingly soluble salts of rare earths should also be insoluble in water and organic solvents, so that they remain in the residue in any case and can then be clearly determined analytically next to one another.

Um die verschiedenen Substanzgruppen homogen im erfindungsgemäßen Markierungsmittel zu verteilen, müssen sie in der Schmelze der Polymeren eingebracht und intensiv vermischt werden. Hierfür haben sich Mischwerkzeuge mit extrem guter Scher- und Knetwirkung bewährt. Einschneckenextruder sind hierfür noch ungeeignet. Zweischneckenextruder sind dann gut geeignet, wenn sie hohe Scherkräfte entwickeln. Bewährt hat sich beispielsweise der Zweischneckenkneter vom Typ ZSK der Firma Werner & Pfleiderer, Stuttgart. Auch der chargenweise arbeitende Zwangsmischer vom Typ Banbury erscheint geeignet zu sein. Die homogenen Gemische werden anschließend granuliert. Die Granulate sollten vorzugsweise Kantenlängen von 2 bis 6 mm aufweisen. Derartige Granulate lassen sich ohne Schwierigkeit zu Pulvern mit einer Korngröße von 100 bis 1 200 !J.m vermahlen. Es ist wünschenswert, relativ enge Korngrößenverteilungen zu erhalten, weil sich Teilchen gleicher Größe unter den Bedingungen der Explosion einheitlicher verhalten als Produkte mit sehr breiter Korngrößenverteilung. Sofern die Kantenlängen der Granulate größer als 6 mm sind, erhält man beim Mahlen Markierungsmittel mit relativ breiter Korngrößenverteilung, was insbesondere bei der Markierung von Sprengstoffen unerwünscht ist. Bei Sprengstoffen hat man mit Markierungsmitteln optimale Ergebnisse erzielt, die aus möglichst einheitlichen Korngrößen im Bereich von 200 bis 600 !J.m liegen. Gewünschtenfalls kann man von dem gemahlenen Produkt durch Sieben die Teilchen besonders großer und besonders kleiner Kantenlänge abtrennen und dadurch eine enge Korngrößenverteilung erreichen. Im übrigen kann die optimale Korngrößenverteilung auch etwas von der Art des zu markierenden Sprengstoffes abhängen, da die Markierungsmittel auch möglichst homogen mit dem jeweiligen Sprengstoff vermischt werden sollten.In order to distribute the different groups of substances homogeneously in the marking agent according to the invention, they must be introduced into the polymer melt and mixed intensively. Mixing tools with extremely good shearing and kneading effects have proven themselves for this. Single screw extruders are still unsuitable for this. Twin-screw extruders are particularly suitable if they develop high shear forces. The ZSK twin-screw kneader from Werner & Pfleiderer, Stuttgart, for example, has proven its worth. The batch mixer Banbury is also suitable. The homogeneous mixtures are then granulated. The granules should preferably have edge lengths of 2 to 6 mm. Such granules can be used without Difficulty in grinding powders with a grain size of 100 to 1 200! Jm. It is desirable to obtain relatively narrow particle size distributions because particles of the same size behave more uniformly under the conditions of the explosion than products with a very wide particle size distribution. If the edge lengths of the granules are greater than 6 mm, marking agents with a relatively broad particle size distribution are obtained during grinding, which is particularly undesirable when marking explosives. In the case of explosives, optimum results have been achieved with marking agents, which are in the range from 200 to 600 μm, given the most uniform particle sizes possible. If desired, the particles of particularly large and particularly small edge lengths can be separated from the ground product by sieving, thereby achieving a narrow grain size distribution. Furthermore, the optimal grain size distribution can also depend somewhat on the type of explosive to be marked, since the marking means should also be mixed with the respective explosive as homogeneously as possible.

Als Kunststoffe hochmolekularer, thermoplastisch verarbeitbarer Polymerer mit geringer Wasseraufnahmefähigkeit, hoher spezifischer Wärme, geringer Wärmeleitfähigkeit und geringem spezifischem Gewicht haben sich insbesondere Polyäthylene, Polypropylene, Polyamide, Polycarbonate, Polyester, Polyoximethylene und Acrylnitrilbutadienstyrolcopolymere bewährt. Diese Polymere lassen sich ohne Zersetzung in geschmolzenem Zustand mit den analytisch nachweisbaren Substanzgruppen homogen vermischen. Sie sind auch geeignet, diese Substanzen über lange Zeit unverändert zu erhalten und ihre analytische Bestimmung zwecks Dekodierung zu ermöglichen. Da die verwendeten Polymere reproduzierbare thermische Eigenschaften besitzen, die mittels Differential-Thermo-Analyse mikroanalytisch bestimmbar sind, können auch diese Kriterien zur Identifizierung und Dekodierung herangezogen werden. Das Molekulargewicht bzw. die Schmelzviskosität der Polymeren sind unkritisch, solange die Polymeren sich thermoplastisch gut verarbeiten lassen, jedoch gegen Wasser und organische Lösungsmittel bie Raumtemperatur ausreichend stabil sind. Die hohe spezifische Wärme und geringe Wärmeleitfähigkeit schützt die in den Kunststoff eingebrachten Substanzen vor der Einwirkung der Explosionshitze. Das geringe spezifische Gewicht gestattet die leichtere Abtrennung der erfindungsgemäßen Markierungsmittel vom Explosionsschutt durch Flüssigkeiten geeigneter spezifischer Dichte.Polyethylenes, polypropylenes, polyamides, polycarbonates, polyesters, polyoximethylenes and acrylonitrile-butadiene-styrene copolymers have proven particularly useful as plastics of high molecular weight, thermoplastically processable polymers with low water absorption, high specific heat, low thermal conductivity and low specific weight. These polymers can be homogeneously mixed with the analytically detectable groups of substances in the molten state without decomposition. They are also suitable for keeping these substances unchanged over a long period of time and for their analytical determination for the purpose of decoding. Since the polymers used have reproducible thermal properties that can be determined microanalytically using differential thermal analysis, these criteria can also be used for identification and decoding. The molecular weight or the melt viscosity of the polymers are not critical as long as the polymers can be processed thermoplastically well, but are sufficiently stable against water and organic solvents at room temperature. The high specific heat and low thermal conductivity protect the substances introduced into the plastic from the effects of the explosion heat. The low specific weight makes it easier to separate the marking agents according to the invention from the explosion debris by means of liquids of a suitable specific density.

Die ferromagnetischen Teile dienen wie gesagt nur zur Abtrennung und Anreicherung der erfindungsgemäßen Markierungsmittel vom Explosionsschutt und nicht zur analytischen Dekodierung. Als ferromagnetische Materialien haben sich insbesondere Eisenpulver mit einer Oberkorngröße von weniger als 60 !J.m bewährt. Derartige Eisenpulver mit einem Reinheitsgehalt von 99,5 % sind beispielsweise unter der Bezeichnung RZ 60 von der Firma Mannesmann-DEMAG erhältlich. Prinzipiell kommen aber auch alle anderen ferromagnetischen Legierungen infrage, sofern sie in Pulverform zur Verfügung stehen. Sofern diese Legierungen relativ seltene Legierungsbestandteile enthalten, können prinzipiell auch diese zur Identifizierung und Dekodierung herangezogen werden.As said, the ferromagnetic parts only serve to separate and enrich the marking agents according to the invention from the explosion debris and not for analytical decoding. Iron powders with an upper grain size of less than 60 .mu.m have proven particularly useful as ferromagnetic materials. Such iron powder with a purity content of 99.5% is available, for example, under the name RZ 60 from Mannesmann-DEMAG. In principle, however, all other ferromagnetic alloys can also be used, provided they are available in powder form. If these alloys contain relatively rare alloy components, these can in principle also be used for identification and decoding.

Die den erfindungsgemäßen Markierungsmitteln zugesetzten Substanzen sollten gegen kurzzeitige Hitzeeinwirkungen von 200 bis 300 °C beständig sein. Als Fluoreszenzpigmente kommen prinzipiell alle solche Pigmente infrage, die sich durch ihr Fluoreszenzspektrum und ihre Eigenfarbe eindeutig voneinander unterscheiden lassen. Beispiele für geeignete Fluoreszenzpigmente sind die von der Firma Industrial Colours Ltd., England, unter der Bezeichnung FLARE 910, orange, green und yellow vertriebenen Pigmente oder die LUMILUX C-Leuchtpigmente der Firma Riedel-de Haen AG, BRD. Als Fluoreszenzstoffe kommen prinzipiell alle in organischen Lösungsmitteln löslichen Fluoreszenzstoffe infrage, die mit Hilfe organischer Lösungsmittel aus den Markierungsmitteln herausgelöst werden können. Die Fluoreszenzstoffe sollten vorsugsweise wasserunlöslich sein, so daß sie nich bereits durch Wasser aus dem Markierungsmittel herausgelöst werden können. Beispiele für geeignete Fluoreszenzstoffe sind die unter den Bezeichnungen UVITEX OB, UVITEX 127 und UVITEX OB-P der Firma Ciba und unter den Bezeichnungen FLUOLITE XNR und FLUOLITE XMP der Firma ICI vertriebenen Produkte. Als Farbpigmente können wiederum alle ausreichend unlöslichen und wärmestabilen Pigmente verwendet werden, deren Emissionsspektrum eindeutig identifizierbar ist. Geeignete Farbstoffpigmente sind z. B. Sicoplast Gelb 12-0190 und Sicoplast rot 32-0300 sowie z. B. die von der Firma ICI unter der Bezeichnung Waxoline vertriebenen Pigmente mit den Farben blau, rubinrot, grün und gelb.The substances added to the marking agents according to the invention should be resistant to brief heat effects of 200 to 300 ° C. In principle, all those pigments that can be clearly distinguished from one another by their fluorescence spectrum and their own color are suitable as fluorescent pigments. Examples of suitable fluorescent pigments are the pigments sold by Industrial Colors Ltd., England, under the name FLARE 910, orange, green and yellow, or the LUMILUX C luminous pigments from Riedel-de Haen AG, FRG. In principle, all fluorescent substances which are soluble in organic solvents and which can be removed from the marking agents with the aid of organic solvents are suitable as fluorescent substances. The fluorescent substances should preferably be water-insoluble so that they cannot already be dissolved out of the marking agent by water. Examples of suitable fluorescent substances are the products sold under the names UVITEX OB, UVITEX 127 and UVITEX OB-P from the company Ciba and under the names FLUOLITE XNR and FLUOLITE XMP from the company ICI. All sufficiently insoluble and heat-stable pigments whose emission spectrum can be clearly identified can in turn be used as color pigments. Suitable dye pigments are e.g. B. Sicoplast yellow 12-0190 and Sicoplast red 32-0300 and z. B. the pigments sold by ICI under the name Waxoline with the colors blue, ruby red, green and yellow.

Als schwerlösliche und hitzestabile Oxide und/oder Salze von selteneren Metallen kommen beispielsweise Titandioxid, Kupferoxid, Zinkoxid, Strontiumcarbonat, Cadmiumsulfid, Antimontrioxid, Bariumsulfat, Lanthantrioxid und Wismuttrioxid infrage. Als Oxide und/oder schwerlösliche Salze der seltenen Erden kommen insbesondere Cer-IV-Oxid sowie die übrigen Oxide und ggf. Oxalate der Lantaniden infrage. Im übrigen können schwerlösliche und hitzestabile Oxide und/oder Salze von allen Metallen, allein oder in Kombination, verwendet werden, sofern sie mikroanalytisch eindeutig, z. B. durch Röntgenfluoreszenzspektrometrie, identifiziert werden können.For example, titanium dioxide, copper oxide, zinc oxide, strontium carbonate, cadmium sulfide, antimony trioxide, barium sulfate, lanthanum trioxide and bismuth trioxide are suitable as sparingly soluble and heat-stable oxides and / or salts of rare metals. Particularly suitable oxides and / or sparingly soluble salts of the rare earths are cerium IV oxide and the other oxides and possibly oxalates of the lantanides. Otherwise, poorly soluble and heat-stable oxides and / or salts of all metals, alone or in combination, can be used, provided that they are microanalytically unique, e.g. B. by X-ray fluorescence spectrometry can be identified.

Die erfindungsgemäßen Markierungsmittel sind prinzipiell geeignet, Substanzen bezüglich ihrer Herkunft, ihrer Zusammensetzung und ihres Herstellungsdatums zu markieren, sofern hieran ein ernsthaftes Interesse besteht. Derartiges Interesse besteht oder entsteht prinzipiell bei Stoffen, die die Sicherheit der Bevölkerung beeinträchtigen können. So können die erfindungsgäßen Markierungsmittel insbesondere zur Identifizierung von pulverförmigen Gütern benutzt werden, bei denen es aus sicherheitstechnischen oder kriminologischen Gründen sinnvoll oder wichtig ist, sie bezüglich Typ, Hersteller und Herstellungsdatum identifizieren zu können. Besondere Bedeutung hat dieses Problem bereits bei Sprengstoffen. Die erfindungsgemäßen Markierungsmittel sollen daher insbesondere zur Markierung von Sprengstoffen verwendet werden.The marking agents according to the invention are in principle suitable for marking substances with regard to their origin, their composition and their date of manufacture, provided there is serious interest in this. In principle, such interest exists or arises in substances that can affect the safety of the population. Thus, the marking means according to the invention can be used in particular for the identification of powdery goods in which it is sensible or important for security reasons or criminological reasons to be able to identify them in terms of type, manufacturer and date of manufacture. This problem is of particular importance already with explosives. The marking agents according to the invention should therefore be used in particular for marking explosives.

In den nachfolgenden Beispielen sind einige typische Ausführungsformen der erfindungsgemäßen Markierungsmittel sowie ihre Herstellung beschrieben. Alle Prozentangaben hierin sind Gewichtsprozente.The following examples describe some typical embodiments of the marking agents according to the invention and their production. All percentages here are percentages by weight.

Beispiel 1example 1

Figure imgb0001
werden als trockenes Pulver in einem Fluidmischer vom Typ Henschel FM 75 mit einem Volumen von 75 I und einer Drehzahl der Mischwerkzeuge von 1 600 UpM eingegeben und 2 Min. durchgemischt. Dieses Gemisch wird in den Eintragsbehälter eines Zweischneckenkneters vom Typ Werner & Pfleiderer ZSK 53 M 50 eingefüllt und bei einer Schneckendrehzahl von 200 UpM und einer Massetemperatur von 170 °C homogenisiert. Das homogenisierte Gemisch wird ausgetragen und granuliert zu zylinderförmigen Granulaten mit einer Kantenlänge vom 4 mm in einer Mahlanlage vom Typ Pallmann PP8 bei einer Trägergastemperatur von max. 40 °C auf eine Oberkorngrenze von 630 µm vermahlen. Das fertige Markierungsmittel besitzt eine Korngrößenverteilung von 80 bis 630 µm bei einem Gewichtsmittelwert von 310 µm. Als Rohstoffe wurden folgende käufliche Materialien verwendet :
Figure imgb0001
 are entered as dry powder in a Henschel FM 75 fluid mixer with a volume of 75 l and a speed of the mixing tools of 1,600 rpm and mixed for 2 minutes. This mixture is introduced into the feed container of a Werner & Pfleiderer ZSK 53 M 50 twin-screw kneader and homogenized at a screw speed of 200 rpm and a melt temperature of 170 ° C. The homogenized mixture is discharged and granulated into cylindrical granules with an edge length of 4 mm in a Pallmann PP8 grinding system at a carrier gas temperature of max. Grind 40 ° C to an upper grain limit of 630 µm. The finished marking agent has a grain size distribution of 80 to 630 µm with a weight average of 310 µm. The following commercially available materials were used as raw materials:

NiederdruckpolyäthylenpulverLow pressure polyethylene powder

ELTEX A 4090 P mit einer Korngrößenverteilung von 30-900 fJ-m, einem Meltindex (2,16 Kp/190 °C) von 9 g/10 min. und einer Dichte (23 °C) von 0,953 g/cm3. ELTEX ist ein Markenzeichen der Firma Solvay, Belgien.ELTEX A 4090 P with a grain size distribution of 30-900 fJ-m, a melt index (2.16 Kp / 190 ° C) of 9 g / 10 min. and a density (23 ° C) of 0.953 g / cm 3. ELTEX is a trademark of Solvay, Belgium.

EisenpulverIron powder

RZ 60 mit einer Oberkorngröße von 60 µm und einer Reinheit von 99,5 %. RZ 60 ist ein Markenzeichen der Firma Mannesmann-DEMAG, B.R.D.RZ 60 with an upper grain size of 60 µm and a purity of 99.5%. RZ 60 is a trademark of Mannesmann-DEMAG, B.R.D.

FluoreszenzpigmentFluorescent pigment

FLARE 910 orange 4, orangene Eigenfarbe. FLARE ist ein Markenzeichen der Firma INDUSTRIAL COLOURS LTD., England.FLARE 910 orange 4, own orange color. FLARE is a trademark of INDUSTRIAL COLORS LTD., England.

Cer-IV-oxidCerium IV oxide

Ein Produkt der Firma MERK, B.R.D. mit einer Reinheit von 99,9 %.A product from MERK, B.R.D. with a purity of 99.9%.

AntimontrioxidAntimony trioxide

TIMONOX-WHITE STAR mit einer Reinheit von 99 %. TIMONOX-WHITE STAR ist ein Markenname der Firma ASSOCIATED LEAD Manufacturers Ltd., England.TIMONOX-WHITE STAR with a purity of 99%. TIMONOX-WHITE STAR is a trademark of ASSOCIATED LEAD Manufacturers Ltd., England.

Beispiel 2Example 2

Folgende trockenen, pulverförmigen Komponenten werden in einem Pflugscharmischer vom Typ Lödige FM 130 D mit einem Volumen von 130 I und einer Drehzahl der Mischwerkzeuge von 1 000 UpM gegeben, während 4 Min. durchgemischt und dann in den Eintragsbehälter eines Planetwalzenextruders vom Typ Battenfeld-EKK PWE 100 EV eingefüllt, dann bei einer Schneckendrehzahl von 30 UpM und einer Massetemperatur von 145 °C homogenisiert, ausgetragen und granuliert :

Figure imgb0002
The following dry, powdery components are placed in a ploughshare mixer of the type Lödige FM 130 D with a volume of 130 l and a speed of the mixing tools of 1,000 rpm, mixed for 4 minutes and then into the feed container of a planetary roller extruder of the type Battenfeld-EKK PWE 100 EV filled in, then homogenized, discharged and granulated at a screw speed of 30 rpm and a melt temperature of 145 ° C:
Figure imgb0002

Die so erhaltenen zylinderförmigen Granulate mit einer Kantenlänge von 3 mm werden gemäß Beispiel 1 auf eine Endfeinheit von 80-630 µm vermahlen.The cylindrical granules thus obtained with an edge length of 3 mm are ground according to Example 1 to a final fineness of 80-630 μm.

Es wurden folgende am Markt erhältliche Rohstofftypen verwendet:The following types of raw materials available on the market were used:

Hochdruck-PolyäthylenpulverHigh pressure polyethylene powder

Coathylene HO 2454, basierend auf Lotrene MD 0707 mit einer Korngrößenverteilung von 80-630 µ.m, einem Meltindex (2,16 Kp/190 °C) von 7 g/10 min. und einer Dichte (23 °C) von 0,924 g/cm3. Coathylene ist ein Markenname der Firma Plast-Labor SA, Schweiz, Lotrene ein Markenname der Firma CdF, Frankreich.Coathylene HO 2454, based on Lotrene MD 0707 with a grain size distribution of 80-630 µ.m, a melt index (2.16 Kp / 190 ° C) of 7 g / 10 min. and a density (23 ° C) of 0.924 g / cm 3 . Coathylene is a trademark of Plast-Labor SA, Switzerland, Lotrene is a trademark of CdF, France.

EisenpulverIron powder

Entspricht Beispiel 1.Corresponds to example 1.

FluoreszenzpigmentFluorescent pigment

Flare 910 yellow 27, gelbe Eigenfarbe, Lieferant wie Beispiel 1.Flare 910 yellow 27, own yellow color, supplier as example 1.

Lanthan-III-OxidLanthanum III oxide

Ein Produkt der Firma Merk, B.R.D. mit einer Reinheit von 99,9 %.A product from Merk, B.R.D. with a purity of 99.9%.

TitandioxidTitanium dioxide

Kronos CL 220 mit einer Reinheit von 92,5 %.Kronos CL 220 with a purity of 92.5%.

Kronos ist ein Markenname der Firma Kronos-Titan GmbH, BRD.Kronos is a brand name of Kronos-Titan GmbH, FRG.

Beispiel 3Example 3

Gemäß Verfahren aus Beispiel 1 (Massetemperatur im Extruder beträgt abweichend 195 °C) wird aus folgenden trockenen, pulverförmigen Komponenten ein zylindrisches Granulat mit 5 mm Kantenlänge hergestellt und gemäß Verfahren aus Beispiel 1 auf eine Endfeinheit von 80-630 µm vermahlen :

Figure imgb0003
According to the process from Example 1 (melt temperature in the extruder is 195 ° C), the following dry, powdery components are used to produce cylindrical granules with an edge length of 5 mm and, according to the process from Example 1, ground to a final fineness of 80-630 µm:
Figure imgb0003

Es wurden folgende am Markt erhältliche Rohstofftypen verwendet :The following types of raw materials available on the market were used:

PolypopylenpulverPolypopylene powder

Moplen FL V 20 mit einer Korngrößenverteilung von 40-450 µm, einem Meltindex (2,16 Kp/230 °C) von 16 g/10 min. und einer Dichte (23 °C) von 0,90 g/cm3.Moplen FL V 20 with a grain size distribution of 40-450 µm, a melt index (2.16 Kp / 230 ° C) of 16 g / 10 min. and a density (23 ° C) of 0.90 g / cm 3 .

Moplen ist ein Markenname der Montedison, Italien.Moplen is a trademark of Montedison, Italy.

EisenpulverIron powder

Entspricht Beispiel 1.Corresponds to example 1.

FluoreszenzpigmentFluorescent pigment

Flare 910 green 8, grüne Eigenfarbe. Lieferant wie Beispiel 1.Flare 910 green 8, own green color. Supplier as example 1.

Ytrium-III-OxidYtrium III oxide

Ein Produkt der Firma Merk, B.R.D. mit einer Reinheit von 99,9%.A product from Merk, B.R.D. with a purity of 99.9%.

Zinkoxidzinc oxide

Ein Produkt der Firma Lehmann & Voss, B.R.D. mit einer Reinheit von 99,5 %.A product from Lehmann & Voss, B.R.D. with a purity of 99.5%.

Beispiel 4Example 4

In analoger Weise wie in Beispiel 1 beschrieben, wurden folgende Komponenten vermischt, homogenisiert, granuliert und vermahlen :

Figure imgb0004
The following components were mixed, homogenized, granulated and ground in an analogous manner to that described in Example 1:
Figure imgb0004

Es wurden folgende am Markt erhältliche Rohstofftypen verwendet :

  • Hochdruck-Polyäthylen-Pulver
  • Wie Beispiel 1.
The following types of raw materials available on the market were used:
  • High pressure polyethylene powder
  • Like example 1.

EisenpulverIron powder

Wie Beispiel 1.Like example 1.

FluoreszenzstoffFluorescent substance

Uvitex OB, ohne Eigenfärbung, aber mit blauer Fluoreszenz bei 435 nm (max. X). Uvitex ist ein Markenname der Firma Ciba-Geigy AG, Schweiz.Uvitex OB, without self-coloring, but with blue fluorescence at 435 nm (max. X). Uvitex is a brand name of the company Ciba-Geigy AG, Switzerland.

FarbpigmentColor pigment

Sicoplast-Gelb 12-0190 mit gelber Eigenfarbe, bestehend aus Cadmium-Zink-Sulfid. Sicoplast ist ein Markenname der Firma BASF, B.R.D.Sicoplast yellow 12-0190 with its own yellow color, consisting of cadmium zinc sulfide. Sicoplast is a trademark of BASF, B.R.D.

StrontiumstearatStrontium stearate

Ein Produkt der Firma Bärlocher AG, B.R.D. mit einer Reinheit von 98 %.A product from Bärlocher AG, B.R.D. with a purity of 98%.

Beispiel 5Example 5

Markierungsmittel gemäß der obigen Beispiele 1 bis 4 wurden in Mengen von 0,05 bis 1 Gew.-% mit Sprengstoffen vermischt. Aus dem Schutt von Probesprengungen wurde mittels Magneten das Markierungsmittel angereichert. Das Gemisch aus Markierungsmittel und anderen ferromagnetischen Schuttbestandteilen wurde durch wässrige Salzlösungen verschiedener Dichte aufgetrennt. Die Fraktion, welche ausschließlich das Markierungsmittel enthielt, wurde auf seine Bestandteile hin analysiert. Es war ohne weiteres möglich, die verschiedenen Markierungsmittel voneinander zu unterscheiden und somit den verwendeten Sprengstoff zu identifizieren.Marking agents according to Examples 1 to 4 above were mixed with explosives in amounts of 0.05 to 1% by weight. The marking agent was enriched from the debris from test explosions using magnets. The mixture of marking agent and other ferromagnetic debris was separated by aqueous salt solutions of different densities. The fraction containing only the labeling agent was analyzed for its components. It was easily possible to differentiate between the different marking agents and thus to identify the explosives used.

Claims (8)

1. A tracer (marking agent) containing
a) at least 1 per cent by weight of iron powder and/or powder of a ferromagnetic alloy and at least two of the following groups of substances :
b) fluorescent pigments ;
c) organic solvent-soluble, water-insoluble fluorescent materials ;
d) colorant pigments ;
e) sparingly soluble and heat-stable oxides and/or salts of rarer metals ;
f) oxides and/or sparingly soluble salts of rare-earth metals ;

in microanalytically well detectable amounts in the form of a homogeneous mixture with a thermoplastic material, characterized in that the thermoplastically processable material is a high molecular weight synthetic materials having a low water absorption capacity, a high specific heat capacity, a low thermal conductivity, and a low specific gravity, more specifically a synthetic material selected from the group consisting of polyethylenes,- polypropylenes, polyamides, polycarbonates, polyesters, polyoxymethylenes and acrylonitrile-butadiene-styrene copolymers.
2. A tracer according to claim 1, characterized in that the melt has been granulated and ground upon cooling.
3. A tracer according to claims 1 or 2, characterized in that the particle size after grinding is from 100 to 1 200 µm.
4. A tracer according to any one of claims 1 to 3, characterized in that
a) the iron powder and/or powder of ferromagnetic alloys is present in an amount of from 3 to 20 % by weight, and at least two of the following substances are present in an amount set forth below :
b) fluorescent pigments in amounts of from 0.1 to 8 % by weight ;
c) fluorescent materials in amounts of from 0.1 to 5 % by weight ;
d) colorant pigments in amounts of from 0.5 to 8 % by weight ;
e) oxides and/or salts of rarer metals in amounts of from 0.5 to 8 % by weight ; and
f) oxides and/or salts of rare-earth elements in amounts of from 0.5 to 5 % by weight.
5. A process for producing a tracer containing
a) at least 1 per cent by weight of iron powder and/or powder of a ferromagnetic alloy and at least two of the following groups of substances :
b) fluorescents pigments ;
c) organic solvent-soluble, water-insoluble fluorescent materials ;
d) colorant pigments ;
e) sparingly soluble and heat-stable oxides and/or salts of rarer metals ;
f) oxides and/or sparingly soluble salts of rare-earth metals ;

in microanalytically well detectable amounts in the form of a homogeneous mixture with a thermoplastic material, characterized in that a high molecular weight synthetic materials having a low water absorption capacity, a high specific heat capacity, a low thermal conductivity, and a low specific gravity, more specifically a synthetic material selected from the group consisting of polyethylenes, polypropylenes, polyamides, polycarbonates, polyesters, polyoxymethylenes and acrylonitrile-butadiene-styrene copolymers, is used as the thermoplastically processable material and the substances a) to f) are introduced into the melt thereof, followed by thorough mixing to form a homogeneous mixture and granulating and grinding said mixture.
6. The process according to claim 5, characterized in that the iron powder or powder of ferromagnetic alloys is present in an amount of from 3 to 20 % by weight, and at least two of the following substances are present in an amount set forth below :
b) fluorescent pigments in amounts of from 0.1 to 8 % by weight ;
c) fluorescent materials in amounts of from 0.1 to 5 % by weight ;
d) colorant pigments in amounts of from 0.5 to 8 % by weight ;
e) oxides and/or salts of rarer metals in amounts of from 0.5 to 8 % by weight ; and
f) oxides and/or salts of rare-earth elements in amounts of from 0.5 to 5 % by weight.
7. The process according to claim 5 or 6, characterized in that the particle size after grinding is from 100 to 1 200 wm.
8. Use of a tracer according to any one of claims 1 through 4 for labelling explosives.
EP83100815A 1982-02-02 1983-01-28 Marking means, method of manufacture and their use in marking explosives Expired EP0085414B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83100815T ATE18818T1 (en) 1982-02-02 1983-01-28 MARKING AGENTS, PROCESS FOR THEIR PRODUCTION AND THEIR USE IN MARKING EXPLOSIVES.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3203373 1982-02-02
DE3203373 1982-02-02

Publications (2)

Publication Number Publication Date
EP0085414A1 EP0085414A1 (en) 1983-08-10
EP0085414B1 true EP0085414B1 (en) 1986-03-26

Family

ID=6154524

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83100815A Expired EP0085414B1 (en) 1982-02-02 1983-01-28 Marking means, method of manufacture and their use in marking explosives

Country Status (14)

Country Link
EP (1) EP0085414B1 (en)
JP (1) JPS58161989A (en)
AT (1) ATE18818T1 (en)
AU (1) AU554601B2 (en)
BR (1) BR8300481A (en)
CA (1) CA1209341A (en)
DE (1) DE3362645D1 (en)
ES (1) ES8604475A1 (en)
FI (1) FI74699C (en)
IE (1) IE830195L (en)
IL (1) IL67767A (en)
NO (1) NO830327L (en)
PT (1) PT76165A (en)
ZA (1) ZA83613B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008058177A1 (en) * 2008-11-20 2010-06-24 Eos Gmbh Electro Optical Systems Method for identifying laser sintering powders
RU2609921C2 (en) * 2012-08-08 2017-02-07 Сипекс С.А. Method of marking explosive substance
DE102017103780A1 (en) 2017-02-23 2018-08-23 Tailorlux Gmbh Method for identifying a material or material mixture

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3301357C1 (en) * 1983-01-18 1984-08-16 Plast-Labor S.A., 1630 Bulle Marking agents, processes for their preparation and their use for marking finely dispersed systems
JPS6099150A (en) * 1983-11-03 1985-06-03 Mitsubishi Rayon Co Ltd Resin composition containing rare earth element and its manufacture
FR2556867B1 (en) * 1983-12-14 1986-06-06 Jalon Michel SECURITY MARKING METHOD, MATERIALS PROVIDED WITH SECURITY MARKS, AND APPLICATIONS THEREOF.
US4654165A (en) * 1985-04-16 1987-03-31 Micro Tracers, Inc. Microingredient containing tracer
AU7357498A (en) * 1997-04-17 1998-11-11 Dow Chemical Company, The Encapsulated vapor-detection and identification tags
WO2005054132A1 (en) * 2003-12-05 2005-06-16 Orica Australia Pty Ltd Tagged polymeric materials and methods for their preparation
AU2004294360B2 (en) * 2003-12-05 2011-06-09 Duluxgroup (Australia) Pty Ltd Tagged polymeric materials and methods for their preparation
JP5550410B2 (en) 2010-03-25 2014-07-16 株式会社キトー Manual chain block
RU2609224C1 (en) * 2012-06-06 2017-01-31 Акционерное общество "СИПЕКС" Explosive marking method
WO2017005882A1 (en) * 2015-07-07 2017-01-12 Institutt For Energiteknikk Tracers
RU2607665C1 (en) * 2015-11-16 2017-01-10 ООО "Глобал Майнинг Эксплозив - Раша" Method for concealed marking of explosive substances (versions)
RU2639791C1 (en) * 2016-10-10 2017-12-22 Михаил Николаевич Оверченко Marking additive to explosive, method of its preparation, method for determination of explosive origin
DE102017221039B4 (en) * 2017-11-24 2020-09-03 Tesa Se Process for the production of a pressure sensitive adhesive based on acrylonitrile-butadiene rubber
DE102019219469A1 (en) * 2019-12-12 2021-06-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Method for producing a labeled polymer, marker, use of the marker and labeled polymer

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US3897284A (en) * 1971-04-30 1975-07-29 Minnesota Mining & Mfg Tagging explosives with organic microparticles
US4053433A (en) * 1975-02-19 1977-10-11 Minnesota Mining And Manufacturing Company Method of tagging with color-coded microparticles
US4131064A (en) * 1977-07-15 1978-12-26 Westinghouse Electric Corp. Tagging particles which are easily detected by luminescent response, or magnetic pickup, or both

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008058177A1 (en) * 2008-11-20 2010-06-24 Eos Gmbh Electro Optical Systems Method for identifying laser sintering powders
RU2609921C2 (en) * 2012-08-08 2017-02-07 Сипекс С.А. Method of marking explosive substance
DE102017103780A1 (en) 2017-02-23 2018-08-23 Tailorlux Gmbh Method for identifying a material or material mixture

Also Published As

Publication number Publication date
AU554601B2 (en) 1986-08-28
IE830195L (en) 1983-08-02
ES519436A0 (en) 1986-02-01
AU1088383A (en) 1983-08-11
IL67767A (en) 1986-01-31
BR8300481A (en) 1983-11-01
FI74699C (en) 1988-03-10
FI74699B (en) 1987-11-30
EP0085414A1 (en) 1983-08-10
ATE18818T1 (en) 1986-04-15
FI830348L (en) 1983-08-03
CA1209341A (en) 1986-08-12
FI830348A0 (en) 1983-02-01
PT76165A (en) 1983-02-01
ES8604475A1 (en) 1986-02-01
NO830327L (en) 1983-08-03
JPS58161989A (en) 1983-09-26
ZA83613B (en) 1983-11-30
DE3362645D1 (en) 1986-04-30

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