EP0085414B1 - Markierungsmittel, Verfahren zu ihrer Herstellung und ihre Verwendung zur Markierung von Sprengstoffen - Google Patents

Markierungsmittel, Verfahren zu ihrer Herstellung und ihre Verwendung zur Markierung von Sprengstoffen 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
European Patent Office
Prior art keywords
weight
amounts
oxides
salts
pigments
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP83100815A
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German (de)
English (en)
French (fr)
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EP0085414A1 (de
Inventor
Wolfgang Weller
Rudolf Dr. Eggimann
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.)
Coathylene SA
Original Assignee
Coathylene SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Coathylene SA filed Critical Coathylene SA
Priority to AT83100815T priority Critical patent/ATE18818T1/de
Publication of EP0085414A1 publication Critical patent/EP0085414A1/de
Application granted granted Critical
Publication of EP0085414B1 publication Critical patent/EP0085414B1/de
Expired legal-status Critical Current

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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.

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  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Prostheses (AREA)
  • Ultra Sonic Daignosis Equipment (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Medicinal Preparation (AREA)
  • Duplication Or Marking (AREA)
  • Road Signs Or Road Markings (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Cephalosporin Compounds (AREA)
EP83100815A 1982-02-02 1983-01-28 Markierungsmittel, Verfahren zu ihrer Herstellung und ihre Verwendung zur Markierung von Sprengstoffen Expired EP0085414B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83100815T ATE18818T1 (de) 1982-02-02 1983-01-28 Markierungsmittel, verfahren zu ihrer herstellung und ihre verwendung zur markierung von sprengstoffen.

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 (de) 1983-08-10
EP0085414B1 true EP0085414B1 (de) 1986-03-26

Family

ID=6154524

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83100815A Expired EP0085414B1 (de) 1982-02-02 1983-01-28 Markierungsmittel, Verfahren zu ihrer Herstellung und ihre Verwendung zur Markierung von Sprengstoffen

Country Status (14)

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

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008058177A1 (de) * 2008-11-20 2010-06-24 Eos Gmbh Electro Optical Systems Verfahren zur Identifizierung von Lasersinterpulvern
RU2609921C2 (ru) * 2012-08-08 2017-02-07 Сипекс С.А. Способ маркировки взрывчатого вещества
DE102017103780A1 (de) 2017-02-23 2018-08-23 Tailorlux Gmbh Verfahren zur Identifizierung eines Materials bzw. Materialgemisches

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3301357C1 (de) * 1983-01-18 1984-08-16 Plast-Labor S.A., 1630 Bulle Markierungsmittel,Verfahren zu ihrer Herstellung und ihre Verwendung zur Markierung von feindispersen Systemen
JPS6099150A (ja) * 1983-11-03 1985-06-03 Mitsubishi Rayon Co Ltd 希土類元素を含有する樹脂組成物およびその製造法
FR2556867B1 (fr) * 1983-12-14 1986-06-06 Jalon Michel Procede de marquage de securite, matieres pourvues de marques de securite, et leurs applications.
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
NZ547675A (en) * 2003-12-05 2010-06-25 Duluxgroup 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 (ja) 2010-03-25 2014-07-16 株式会社キトー 手動チェーンブロック
RU2609224C1 (ru) * 2012-06-06 2017-01-31 Акционерное общество "СИПЕКС" Способ маркировки взрывчатого вещества
WO2017005882A1 (en) * 2015-07-07 2017-01-12 Institutt For Energiteknikk Tracers
RU2607665C1 (ru) * 2015-11-16 2017-01-10 ООО "Глобал Майнинг Эксплозив - Раша" Способ скрытой маркировки взрывчатых веществ (варианты)
RU2639791C1 (ru) * 2016-10-10 2017-12-22 Михаил Николаевич Оверченко Маркирующая добавка во взрывчатое вещество, способ ее приготовления, способ определения происхождения взрывчатого вещества
DE102017221039B4 (de) * 2017-11-24 2020-09-03 Tesa Se Verfahren zur Herstellung einer Haftklebemasse auf Basis von Acrylnitril-Butadien-Kautschuk
DE102019219469A1 (de) * 2019-12-12 2021-06-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Herstellung eines markierten Polymers, Marker, Verwendung des Markers und markiertes Polymer

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (de) * 2008-11-20 2010-06-24 Eos Gmbh Electro Optical Systems Verfahren zur Identifizierung von Lasersinterpulvern
RU2609921C2 (ru) * 2012-08-08 2017-02-07 Сипекс С.А. Способ маркировки взрывчатого вещества
DE102017103780A1 (de) 2017-02-23 2018-08-23 Tailorlux Gmbh Verfahren zur Identifizierung eines Materials bzw. Materialgemisches

Also Published As

Publication number Publication date
NO830327L (no) 1983-08-03
IE830195L (en) 1983-08-02
IL67767A (en) 1986-01-31
ES519436A0 (es) 1986-02-01
ES8604475A1 (es) 1986-02-01
FI74699B (fi) 1987-11-30
EP0085414A1 (de) 1983-08-10
CA1209341A (en) 1986-08-12
PT76165A (en) 1983-02-01
ZA83613B (en) 1983-11-30
AU554601B2 (en) 1986-08-28
FI74699C (fi) 1988-03-10
FI830348L (fi) 1983-08-03
JPS58161989A (ja) 1983-09-26
FI830348A0 (fi) 1983-02-01
ATE18818T1 (de) 1986-04-15
DE3362645D1 (en) 1986-04-30
AU1088383A (en) 1983-08-11
BR8300481A (pt) 1983-11-01

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