EP2466561A1 - Kit de coloration pour colorer des objets de valeur, appareil et procédé - Google Patents

Kit de coloration pour colorer des objets de valeur, appareil et procédé Download PDF

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Publication number
EP2466561A1
EP2466561A1 EP10195407A EP10195407A EP2466561A1 EP 2466561 A1 EP2466561 A1 EP 2466561A1 EP 10195407 A EP10195407 A EP 10195407A EP 10195407 A EP10195407 A EP 10195407A EP 2466561 A1 EP2466561 A1 EP 2466561A1
Authority
EP
European Patent Office
Prior art keywords
adhesive
composition
colorant
staining
kit according
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.)
Withdrawn
Application number
EP10195407A
Other languages
German (de)
English (en)
Inventor
Weidong He
Long Lin
John Ruthven
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.)
G4S Cash Solutions UK Ltd
Original Assignee
G4S Cash Solutions UK Ltd
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 G4S Cash Solutions UK Ltd filed Critical G4S Cash Solutions UK Ltd
Priority to EP10195407A priority Critical patent/EP2466561A1/fr
Publication of EP2466561A1 publication Critical patent/EP2466561A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • E—FIXED CONSTRUCTIONS
    • E05—LOCKS; KEYS; WINDOW OR DOOR FITTINGS; SAFES
    • E05G—SAFES OR STRONG-ROOMS FOR VALUABLES; BANK PROTECTION DEVICES; SAFETY TRANSACTION PARTITIONS
    • E05G1/00—Safes or strong-rooms for valuables
    • E05G1/14—Safes or strong-rooms for valuables with means for masking or destroying the valuables, e.g. in case of theft

Definitions

  • the invention relates to a staining kit for staining valuables, in particular banknote paper, and an apparatus and method for staining valuables.
  • Dye systems are also known, for instance known from US 5,196,828 .
  • US 5,156,272 shows a banknote transport case having a dye system spilling dye on banknotes after an unauthorized breach of the case, leaving the banknotes useless.
  • WO2008/072193 shows a more advanced dye/pigment-based system, using dyes/pigments combined with a resin system, making it more difficult to remove the dyes/pigments from banknotes afterwards.
  • This system uses methacrylates as the resin binder combined with a number of commercially available dyes/pigments.
  • the invention provides a staining kit for staining valuables, in particular banknote paper, comprising; at least one adhesive composition, comprising polymerizable adhesive monomers capable of forming a polymer adhesive upon activation; at least one colorant composition, comprising at least one colorant, capable of yielding an adhesive-bound colorant with the adhesive composition; and at least one adhesive crosslinker, capable of activating the adhesive monomers when contacted with the adhesive composition.
  • the adhesive crosslinker accellerates the polymerization reaction, thus allowing for rapid formation of the polymer adhesive on the valuables to be stained.
  • at least the adhesive composition and the adhesive crosslinker should be kept separated.
  • the colorant composition is usually also kept separated from the adhesive composition, as during storage unwanted reactions may occur. When triggered, for instance in case of burglary or an alarm signal, all components of the kit are to be applied essentially simultaneously on the valuables to be stained. Upon mixing the adhesive formulation with the colorant composition and the adhesive crosslinker, rapidly an adhesive-bound colorant is formed on the valuables.
  • the adhesive composition and/or the colorant composition are liquid compositions. Appropriate solvents may be added in order to fully dissolve the ingredients.
  • the at least one adhesive crosslinker is comprised in the colorant composition.
  • the staining kit would only need two separate compositions, allowing for a more compact storage and easier simultaneous application to the valuables to be stained.
  • the at least one adhesive crosslinker comprises an alcohol, acid or ether.
  • Alcohols, acids and/or ethers function well as an crosslinker and accellerator for the polymerization reaction of the adhesive. These are particularly suitable for activating cyanoacrylate polymerization.
  • the crosslinker is liquid at ambient temperature (20 °C), and is essentially non-volatile, typically having a vapor pressure below 20 kPa at 20 °C and a boiling point higher than water (100 °C at 1 atm).
  • Epoxides are preferred as adhesive crosslinkers.
  • Other suitable crosslinkers include ethanol, propanol, propionic acid, and acetic acid.
  • a particularly suitable adhesive crosslinker comprises glycerol propoxylate triglycidyl ether. This compound is essentially non-volatile, having a boiling point of 149 °C, dissolves in most solvents, and readily starts up polymerization when contacted with adhesive monomers, in particular cyanoacrylates.
  • Alternative suitable crosslinkers include poly(ethylene glycol) diglycidyl ether, and Tris(2,3-epoxypropyl) isocyanurate.
  • the colorant composition is a liquid composition using a C1-4 lower alkyl alcohol as a solvent, preferably ethanol.
  • a C1-4 lower alkyl alcohol as a solvent, preferably ethanol.
  • Lower alkyl alcohols have proven to be very efficient in rapidly spreading the colorant composition over valuables, in particular various types of banknote paper.
  • the adhesive monomers are selected from the group consisting of urethanes, epoxides and cyanoacrylates.
  • urethanes epoxides
  • cyanoacrylates epoxides
  • these types of polymerizable adhesives have proven to be very efficient in binding colorants to valuables, in particular to banknotes. It is also possible to use a mixture of different monomers, yielding copolymers of urethanes, epoxides and/or cyanoacrylates.
  • the polymerizable adhesive comprises cyanoacrylate polymerizable monomers.
  • Cyanoacrylates have proven to bind colorants rapidly to valuables, in particular banknote paper, and are difficult to remove. Another advantage is that cyanoacrylate has a relatively low toxicity for humans.
  • Suitable commercially available cyanoacrylate monomers are methyl 2-cyanoacrylate, ethyl 2-cyanoacrylate, n-propyl 2-cyanoacrylate, isopropyl 2-cyanoacrylate, tert-butyl 2-cyanoacrylate, n-butyl 2-cyanoacrylate, isobutyl 2-cyanoacrylate, 3-methoxybutyl cyanoacrylate, n-decyl cyanoacrylate, hexyl 2-cyanoacrylate, 2-ethoxyethyl 2-cyanoacrylate, 2-methoxyethyl 2-cyanoacrylate, 2-octyl 2-cyanoacrylate, 2-propoxyethyl 2-cyanoacrylate, n-octyl 2-cyanoacrylate, and isoamyl cyanoacrylate. These compounds may be used as pure monomers, or as mixed monomers to yield cyanoacrylate copolymers after polymerization.
  • cyanoacrylate-based adhesives Whilst performing well in terms of permanence of bonding, cyanoacrylate-based adhesives may suffer from lack of resistance to organic solvents such as acetone, which is an intrinsic solvent for most cross-linked cyanoacrylate based systems.
  • organic solvents such as acetone
  • Other problems associated with the cyanoacrylate-based systems are the relatively slow diffusion of the adhesive through paper-based banknotes, particularly those carrying a protective varnish layer.
  • the adhesive monomer comprises a C1-C4 alkyl cyanoacrylate.
  • These monomers selected from the group consisting of methyl 2-cyanoacrylate, ethyl 2-cyanoacrylate, n-propyl 2-cyanoacrylate, isopropyl 2-cyanoacrylate, tert-butyl 2-cyanoacrylate, n-butyl 2-cyanoacrylate and isobutyl 2-cyanoacrylate show a faster spreading over the surface and into porous materials, in particular various types of banknote paper.
  • the colorant comprises a disperse dye and/or a cationic dye.
  • Disperse dyes and cationic dyes enable intense staining of valuables. It is preferred if a mix of different types of dyes is used, as this makes it more difficult to remove the stain from the valuables.
  • the colorant comprises a disperse dye and/or a cationic dye, combined with at least one dye coupling agent.
  • Dye coupling agents react with the dyes to form a plethora of chemically modified dyes with different colour and binding properties, making it even harder to remove the dyes.
  • the colorant comprises a disperse dye selected from the group consisting of Serilene Black SG Grains, Serilene Black T-LS 200, Serilene Brown 2B-LSN, Serilene B. Blue K-BGF, and Serilene Scarlet G-LS150, as supplied by Brunswick Group. These dyes have shown excellent staining results.
  • the colorant comprises at least one cationic dye selected from the group consisting of Brilliant Green, Brilliant Blue RL, and Dark Brown X-3RL, as supplied by Zhejiang Runtu Ltd. These cationic dyes have shown excellent staining results.
  • the cationic dye is admixed with an acid. Adding an acid provides a better binding of the cationic dye to certain types of valuables, in particular porous types of banknote paper.
  • the dye coupling agent compound is selected from the group consisting of phenols, disubstituted phenylenediamines and phenyleneaminophenols, and resorcinol derivatives.
  • Preferred dye coupling agents are 1,3-phenylenediamine (m-phenylenediamine), 1,4-phenyldiamine (p-phenyldiamine), resorcin, 4-chlororesorcin, 1-naphtol, 3-aminophenol and 5-amino-2-methylphenol.
  • Disubstituted phenyldiamines, in particular 1,3-phenylenediamine, 1,4-phenyldiamine are most preferred for use in bank note staining systems.
  • the dye coupling agents react with sodium bromate to form pigments inside the paper fibre matrix giving permanent staining.
  • the cationic dye present is actually made darker.
  • the pigment formed and the dye contained in the adhesive will stain the whole banknote making the removal of the stain even harder.
  • the bank note staining system according to the invention is much harder to overcome than known bank note staining systems.
  • the invention further provides an apparatus for staining valuables, in particular bank notes, using a kit according to the invention, wherein the apparatus comprises at least one first compartment comprising a colorant composition, at least one second compartment comprising an adhesive composition, and trigger means for applying the adhesive composition and the colorant composition from the first and second compartments as a mix onto valuables to be stained upon receiving a trigger signal.
  • the apparatus may be integrated in for instance a cash dispenser machine, a money transport and/or storage container or vehicle.
  • the inventions also provides a method for staining valuables, in particular bank notes, using a kit according to the invention, comprising the steps of providing valuables, preferably bank notes; providing at least one adhesive composition, comprising reactive adhesive monomers capable of forming a polymer adhesive upon activation; providing at least one colorant composition, comprising at least one colorant, capable of forming yield an adhesive-bound colorant with the adhesive composition; providing at least one adhesive crosslinker, separated from the adhesive composition, for activating the adhesive monomers when contacted with the adhesive composition; wherein upon a trigger signal, the adhesive composition, the colorant composition and the adhesive crosslinker are applied to the valuables to be stained, forming an adhesive bound colorant on the valuables.
  • the examples show two different dye compositions, used as a first pack which may be combined with a second pack comprising an adhesive to form a banknote neutralisation system.
  • the compositions shown in the examples are particularly suitable for use with a cyanoacrylate adhesive for permanently staining banknotes.
  • These dye compositions may be applied in for instance cash dispenser machines or cash transport containers, having at least one first compartment for the dye composition, at least one second compartment for the adhesive composition, and a triggered mechanism designed to apply the adhesive and dye as a mix onto the banknotes to be neutralized upon receiving a trigger signal.
  • a coloured resin or glue will be formed that upon contact will spoil the money stored in the cassette. This is used as a security measure.
  • the trigger mechanism may for instance be a remote control or an automated alarm. Examples of suitable mechanisms are for instance described in EP 1 298 276 and US 5 598 793 , that are incorporated herein by reference.
  • Serilene Black SG and Brilliant Green act as staining dyes.
  • 1-methyl-2-pyrrolidinone is a solvent for the dispersed dyes.
  • Glycerol propoxylate triglycidyl ether is the crosslinker for crosslinking the dyes with the adhesive.
  • Ethanol is a solvent for cationic dye.
  • Hydrochloric acid (37%) acts as a colour enhancer for cationic dye.
  • 1,3-phenylene diamine (or alternatively 1,4 -phenylene diamine), sodium bromate and half of the propionic acid were mixed under stirring and heating at 65°C for 60 minutes.
  • the mixture was cooled to ambient temperature and subsequently, Brilliant Green was added.
  • the mixture was stirred until complete dissolution of Brilliant Green, followed by addition of the remaining propionic acid and water while stirring.
  • the mixture was filtered to obtain the dye formulation as the filtrate.
  • Brilliant Green is the staining dye.
  • M-phenylenediamine and p-phenylenediamine are precursors of the pigment.
  • Propionic acid acts as a solvent/solubiliser for the phenylenediamines.
  • Sodium bromate is an oxidant for pigment formation, oxidizing the phenylene diamines into reactive species.
  • Water is the preferred solvent for the cationic dye.
  • Solvent Test result Solvent Test Result Ethoxypropanol +++ DMF + 1,2-dichlorobenzene ++ THF +++ Isolbutylmehthylketone ++ N-methylpyrollidone +++ Cyclohexanone ++ Toluene +++ Methanol ++ Dimethyl sulfoxide +++ Ethanol ++ Sodium hypochlorde +++ 2-methoxyethanol ++ Dipropylene glycol monomethylether +++ Acetone + hexane +++ Ethyl acetate +++
  • Composition 2 showed a solvent resitance that was at least similar and for some solvents better than composition I. Both sytems I and II are however very suitable for bank note staining systems. The better resistance is believed to be due to a faster crosslinking reaction with the bank note material observed for composition 2, which is believed to be due to the presence of the diamines. With some of the solvents, in particular acetone, ethyl acetate, isobutyl methyl ketone, THF, methoxyethanol, ethoxypropanol and toluene, the colour is actually spread more through the bank note material rather than being washed out, actually achieving a more wide-spread colouring than after the initial staining. Interestingly, oxidative solutions, in this case bleach, changed the colouring to a deep black. The compostion also showed a strong resistance to caustic soda, changing the colour to a dark brown.

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  • Adhesives Or Adhesive Processes (AREA)
EP10195407A 2010-12-16 2010-12-16 Kit de coloration pour colorer des objets de valeur, appareil et procédé Withdrawn EP2466561A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10195407A EP2466561A1 (fr) 2010-12-16 2010-12-16 Kit de coloration pour colorer des objets de valeur, appareil et procédé

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP10195407A EP2466561A1 (fr) 2010-12-16 2010-12-16 Kit de coloration pour colorer des objets de valeur, appareil et procédé

Publications (1)

Publication Number Publication Date
EP2466561A1 true EP2466561A1 (fr) 2012-06-20

Family

ID=44021997

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10195407A Withdrawn EP2466561A1 (fr) 2010-12-16 2010-12-16 Kit de coloration pour colorer des objets de valeur, appareil et procédé

Country Status (1)

Country Link
EP (1) EP2466561A1 (fr)

Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59152454A (ja) * 1983-02-18 1984-08-31 Canon Inc 静電荷像現像用トナ−の製造方法
US5156272A (en) 1990-07-26 1992-10-20 Fichet Bauche Device for defacing valuable documents and cases for automatic banknote dispensers fitted with such device
US5196828A (en) 1992-01-14 1993-03-23 U.S. Currency Protection Corp. Bendable currency security dye pack
US5405599A (en) 1994-02-22 1995-04-11 Porrovecchio; Dennis J. Method and composition for deterring criminals
US5598793A (en) 1993-06-17 1997-02-04 Lopez, Jr.; Martin ATM anti-theft device
DE19619420A1 (de) * 1996-05-14 1997-11-20 Rathor Ag Vorrichtung zur Erzeugung reaktiver Massen für den Objektschutz
GB2330586A (en) * 1997-10-27 1999-04-28 Scott Bader Co Aqueous pigment printing paste composition
WO1999045514A1 (fr) * 1998-03-03 1999-09-10 Tracking Technologies, Inc. Compositions de marquage pouvant etre identifiees et procedes
WO2001098616A2 (fr) * 2000-06-20 2001-12-27 I & S Technologies Bvba Composition de degradation de billets de banque, de titres et autres objets de valeur
CN1347947A (zh) * 2000-10-09 2002-05-08 天津市天龙贸易公司 水乳型低温真皮彩色罩印粘合剂
EP1298276A2 (fr) 1997-12-31 2003-04-02 Fluiditi Limited Système de sécurité
KR20030079165A (ko) * 2002-04-02 2003-10-10 한국화학연구원 잉크용 착색 수지의 수성 분산체
WO2008072193A2 (fr) 2006-12-15 2008-06-19 Liquid Colours (Pty) Ltd Composition de sécurité
JP2008156463A (ja) * 2006-12-22 2008-07-10 Kao Corp 架橋コアシェルポリマー粒子の分散体の製造方法
EP2000622A1 (fr) * 2007-06-06 2008-12-10 Petersen-Bach A/S Système de sécurité pour sécuriser des objets de valeur
JP2008308646A (ja) * 2007-06-18 2008-12-25 Three M Innovative Properties Co 着色されたアクリル系粘着剤及びマーキングフィルム
US20090043036A1 (en) * 2007-08-09 2009-02-12 Samsung Electronics Co., Ltd. Capsulated colorant, method of preparing the same, and ink composition including the capsulated colorant
US20090286250A1 (en) * 2006-05-19 2009-11-19 James Arthur Hayward Incorporating soluble security markers into cyanoacrylate solutions
EP2239304A1 (fr) * 2007-12-20 2010-10-13 Matsui Shikiso Chemical Co., Ltd. Composition colorante

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59152454A (ja) * 1983-02-18 1984-08-31 Canon Inc 静電荷像現像用トナ−の製造方法
US5156272A (en) 1990-07-26 1992-10-20 Fichet Bauche Device for defacing valuable documents and cases for automatic banknote dispensers fitted with such device
US5196828A (en) 1992-01-14 1993-03-23 U.S. Currency Protection Corp. Bendable currency security dye pack
US5598793A (en) 1993-06-17 1997-02-04 Lopez, Jr.; Martin ATM anti-theft device
US5405599A (en) 1994-02-22 1995-04-11 Porrovecchio; Dennis J. Method and composition for deterring criminals
DE19619420A1 (de) * 1996-05-14 1997-11-20 Rathor Ag Vorrichtung zur Erzeugung reaktiver Massen für den Objektschutz
GB2330586A (en) * 1997-10-27 1999-04-28 Scott Bader Co Aqueous pigment printing paste composition
EP1298276A2 (fr) 1997-12-31 2003-04-02 Fluiditi Limited Système de sécurité
WO1999045514A1 (fr) * 1998-03-03 1999-09-10 Tracking Technologies, Inc. Compositions de marquage pouvant etre identifiees et procedes
WO2001098616A2 (fr) * 2000-06-20 2001-12-27 I & S Technologies Bvba Composition de degradation de billets de banque, de titres et autres objets de valeur
CN1347947A (zh) * 2000-10-09 2002-05-08 天津市天龙贸易公司 水乳型低温真皮彩色罩印粘合剂
KR20030079165A (ko) * 2002-04-02 2003-10-10 한국화학연구원 잉크용 착색 수지의 수성 분산체
US20090286250A1 (en) * 2006-05-19 2009-11-19 James Arthur Hayward Incorporating soluble security markers into cyanoacrylate solutions
WO2008072193A2 (fr) 2006-12-15 2008-06-19 Liquid Colours (Pty) Ltd Composition de sécurité
JP2008156463A (ja) * 2006-12-22 2008-07-10 Kao Corp 架橋コアシェルポリマー粒子の分散体の製造方法
EP2000622A1 (fr) * 2007-06-06 2008-12-10 Petersen-Bach A/S Système de sécurité pour sécuriser des objets de valeur
JP2008308646A (ja) * 2007-06-18 2008-12-25 Three M Innovative Properties Co 着色されたアクリル系粘着剤及びマーキングフィルム
US20090043036A1 (en) * 2007-08-09 2009-02-12 Samsung Electronics Co., Ltd. Capsulated colorant, method of preparing the same, and ink composition including the capsulated colorant
EP2239304A1 (fr) * 2007-12-20 2010-10-13 Matsui Shikiso Chemical Co., Ltd. Composition colorante

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