EP0632162B1 - Gegen Einwirkung chemischer Verbindungen fälschungssicheres Blatt und daraus hergestelltes fälschungssicheres Dokument - Google Patents

Gegen Einwirkung chemischer Verbindungen fälschungssicheres Blatt und daraus hergestelltes fälschungssicheres Dokument Download PDF

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Publication number
EP0632162B1
EP0632162B1 EP94400090A EP94400090A EP0632162B1 EP 0632162 B1 EP0632162 B1 EP 0632162B1 EP 94400090 A EP94400090 A EP 94400090A EP 94400090 A EP94400090 A EP 94400090A EP 0632162 B1 EP0632162 B1 EP 0632162B1
Authority
EP
European Patent Office
Prior art keywords
acid
chosen
acids
sheet according
salts
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 - Lifetime
Application number
EP94400090A
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English (en)
French (fr)
Other versions
EP0632162A1 (de
Inventor
Alain Barthez
Sandrine Dubois
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.)
ArjoWiggins SAS
Original Assignee
ArjoWiggins SAS
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
Priority claimed from FR9307885A external-priority patent/FR2694772B1/fr
Application filed by ArjoWiggins SAS filed Critical ArjoWiggins SAS
Publication of EP0632162A1 publication Critical patent/EP0632162A1/de
Application granted granted Critical
Publication of EP0632162B1 publication Critical patent/EP0632162B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/46—Elements suited for chemical verification or impeding chemical tampering, e.g. by use of eradicators

Definitions

  • the present invention relates to a falsifiable sheet by chemical agents as well as the safety document obtained and the use of a product as a co-reactant. It relates more particularly to the field of paper safety usable especially for the production of parts of payment or official documents such as checks banking, traveller's checks, accounting ledgers, titles, notarial acts, tickets, and in general all documents for which it is essential to protect against any chemical falsification of writings or seals entered on these said documents.
  • the object of the invention is to provide a security sheet containing a salt as a chemical forging agent metallic, the sensitivity of this salt towards agents of falsification being improved, that is to say that the reactions will be more intense than with salt alone or colored reactions will take place when they do not exist, in any case imperceptible with salt alone.
  • a further aim is to provide a sheet protected against the greatest number of chemical falsification agents while using as few reagents as possible tampering.
  • metal salt a co-reactant chosen in the group formed by certain organic acids or their salts, some derivatives of organic acid, compounds having a function aldehyde reducing agent, the compounds having a reducing function ketone, precursors of carbon dioxide.
  • the invention provides a sheet which cannot be forged by agents.
  • chemicals comprising at least one means of tampering of which at least one of these means consists of a metal salt associated with a coreagent, characterized by the fact that the coreactive is chosen from the group formed by acids organic as defined in claim 1 or their salts, organic acid derivatives as defined in claim 1, the compounds having a reducing function aldehyde, the compounds having a ketone reducing function, carbon dioxide precursors, being excluded from this groups the compounds comprising a phenolic structure.
  • the metal salt is chosen from the salts of cobalt II or III, nickel salts or their mixtures.
  • metallic salts they can in particular be chosen among chlorides, sulfates, acetates, nitrates, these salts being anhydrous or hydrated.
  • amino acids or sulfonic acids have at least two acid groups. These groupings can be identical, for example the acid cannot contain only carboxylic groups, only sulfonic groups.
  • the acid can have both carboxylic groups and sulfonic (s).
  • the carboxylic acid is chosen from the group formed by tartaric acid, phthalic acid, acid citric, malonic acid, tricarballylic acid, acid trimelittic.
  • the organic acid derivatives are chosen from amides, lactams, anhydrides or even acid chlorides.
  • the anhydrides can be of the purely carboxylic or purely sulfonic type or of the mixed type, for example of the sulfocarboxylic type, formed between the carboxylic and sulfonic acid groups.
  • the anhydride is of the sulfocarboxylic type, in particular it is 2-sulfo-benzoic anhydride.
  • the organic acid can be chosen from amino acids, and more particularly among glutamic acids or asparagines.
  • butyraldehyde Preferably used as a compound having a function aldehyde reducing agent, butyraldehyde.
  • the carbon dioxide precursor is a carbonate or bicarbonate, such as carbonate or sodium bicarbonate.
  • the unforgeable sheet is a paper of purely cellulosic fibrous composition, in part synthetic or possibly purely synthetic.
  • Leaf may still be a plastic film, possibly coated.
  • the composition of the sheet may contain agents classics used in stationery such as fillers minerals, binders, various resistance agents, bonding products, shading dyes.
  • the chemical falsification reagents according to the invention can be added en masse to the composition of the sheet or placed on at least one face of the sheet by impregnation or by coating.
  • reagents that are soluble in water or in non-or very weakly toxic solvents or in their mixtures are used, these reagents being applied to the sheet by impregnation using a size press.
  • the sheet can also include physical authentication elements such as watermarks, plates, threads or special fibers.
  • the sheet is printable by any means of printing and is suitable for writing, in particular with an ink pen or with a ballpoint pen.
  • the invention also relates to the security document obtained from of the unforgeable sheet described above as well as the use as defined in claims 11 and 12.
  • the wet recovery of the solution is approximately 40 g per 100 g of paper.
  • Example 1 To 100 g of the solution of Example 1, 2 g of an organic acid which is malonic acid is added. The sheet is treated as in Example 1.
  • the reactivity of the sheets obtained according to these examples is tested comparatively by using a saturated sodium sulfite solution as a falsifying agent.
  • a saturated sodium sulfite solution as a falsifying agent.
  • an orange coloration is obtained which is more intense than that obtained for example 1.
  • Malonic acid therefore participated in the colored reaction between the cobalt salt and the falsifying agent.
  • Example 2 A solution is made as in Example 2, but the acid used is a mineral acid, sulfuric acid.
  • the colored reaction under the action of a saturated sulfite solution is not more intense than in Example 1.
  • Aqueous solutions are produced as in Example 2, the organic acid being a dicarboxylic acid chosen from glutaric acid, citric acid, phthalic acid or tartaric acid, the amount of acid varying between 0 , 5 and 2.5 g per 100 g of the bath of Example 1.
  • Example 2 A solution is made as in Example 2, but the cobalt salt is replaced by nickel chloride.
  • the co-reactant of the cobalt salt is an amino acid, either L-glutamic acid which has two carboxyl groups, or L-asparagine which has only one carboxyl group.
  • L-glutamic acid which has two carboxyl groups
  • L-asparagine which has only one carboxyl group.
  • Example 2 A solution is produced as in Example 2, but cobalt salt, tricarboxylic acid derived from propane, called tricarballylic acid, is used as co-reactant.
  • cobalt salt tricarboxylic acid derived from propane, called tricarballylic acid.
  • the potassium permanganate / sodium bisulfite redox couple is applied, there is also an orange coloring, while in the case of Example 1 (case of the cobalt salt alone) there is no clearly visible colored reaction. .
  • Example 2 A solution is made as in Example 2, but the acid used is benzoic acid 1,2,4 tricarboxylic called trimelittic acid.
  • the acid used is benzoic acid 1,2,4 tricarboxylic called trimelittic acid.
  • trimelittic acid we treat a paper as in Example 2. The paper is tested with a saturated sodium sulfite solution, it develops an orange coloring.
  • Example 2 To 100 g of the solution of Example 1, 1.45 g of 2-sulfo-benzoic anhydride (mixed anhydride formed between the carboxylic and sulfonic groups) is added. We impregnate a sheet and dry it. The leaf obtained is tested with a saturated sodium sulfite solution, an intense orange reaction develops.
  • 2-sulfo-benzoic anhydride mixed anhydride formed between the carboxylic and sulfonic groups
  • a plastic sheet is coated with this composition, the quantity deposited dry being 10 g / m 2 .
  • the sheet Under the action of a saturated solution of sodium sulfite it develops an orange coloring. Under the action of the potassium permanganate / sodium bisulfite couple, a greenish-brown reaction develops.
  • Example 2 To 100 g of the solution of Example 1, 1.7 g of tartaric acid and 1 g of manganese sulphate are added (manganese sulphate is a forging agent known for its reactivity with bleach).
  • manganese sulphate is a forging agent known for its reactivity with bleach.
  • sulfite Under the action of sulfite, an intense orange color is obtained, bisulfite an orange color, bleach a brown color, sodium hydroxide a brown color, an ink eraser pencil, an orange color , CORECTOR ink a pink to orange halo.

Landscapes

  • Paper (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Claims (12)

  1. Gegen Fälschung mit chemischen Reagenzien sicheres Blatt mit mindestens einem Fälschungssicherungsmittel, wobei mindestens eines dieser Mittel aus einem Metallsalz in Assoziation mit einem Coreagenz besteht, dadurch gekennzeichnet, daß es sich bei dem Coreagenz um eine Verbindung aus der Gruppe bestehend aus:
    unter Carbonsäuren mit mindestens zwei sauren Gruppierungen, Sulfonsäuren, Aminosäuren sowie Salzen dieser Säuren ausgewählten organischen Säuren,
    Derivaten organischer Säuren, ausgewählt unter Amiden, Lactamen, Anhydriden und Säurechloriden,
    Verbindungen mit einer reduzierend wirkenden Aldehydfunktion,
    Verbindungen mit einer reduzierend wirkenden Ketofunktion und
    Kohlendioxid-Vorläufern
    mit Ausnahme von Verbindungen mit einer Phenolstruktur
    handelt.
  2. Blatt nach Anspruch 1, dadurch gekennzeichnet, daß das Metallsalz unter Cobalt(II)- oder Cobalt(III)-Salzen, Nickelsalzen oder deren Gemischen ausgewählt wird.
  3. Blatt nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Metallsalze unter den Nitraten, Chloriden, Sulfaten und Acetaten ausgewählt sind und wasserfrei oder hydratisiert sind.
  4. Blatt nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Sulfonsäuren oder Aminosäuren mindestens zwei sauren Gruppierungen enthalten.
  5. Blatt nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Carbonsäuren aus der Gruppe bestehend aus Malonsäure, Glutarsäure, Phthalsäure, Citronensäure, Weinsäure, Tricarballylsäure und Trimellitsäure ausgewählt sind.
  6. Blatt nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es sich bei dem Anhydrid um 2-Sulfobenzoesäureanhydrid handelt.
  7. Blatt nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Aminosäuren unter den Glutaminsäuren oder den Asparaginen ausgewählt sind.
  8. Blatt nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es sich bei der Verbindung mit einer reduzierend wirkenden Aldehydfunktion um Butyraldehyd handelt.
  9. Blatt nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es sich bei den Kohlendioxid-Vorläufern um Carbonate oder Hydrogencarbonate, insbesondere Natriumcarbonat oder -hydrogencarbonat, handelt.
  10. Fälschungssicheres Dokument, dadurch gekennzeichnet, daß es aus einem Blatt nach einem der vorhergehenden Ansprüche erhalten wird.
  11. Verwendung eines Produkts aus der Klasse aus:
    unter Carbonsäuren mit mindestens zwei sauren Gruppierungen, Sulfonsäuren, Aminosäuren sowie Salzen dieser Säuren ausgewählten organischen Säuren,
    Derivaten organischer Säuren, ausgewählt unter Amiden, Lactamen, Anhydriden und Säurechloriden,
    Verbindungen mit einer reduzierend wirkenden Aldehydfunktion,
    Verbindungen mit einer reduzierend wirkenden Ketofunktion und
    Kohlendioxid-Vorläufern
    mit Ausnahme von Verbindungen mit einer Phenolstruktur
    als Coreagenz zur Verbesserung der Empfindlichkeit eines als Fälschungssicherungsmittel für ein Blatt eingesetzten Metallsalzes.
  12. Verwendung nach Anspruch 11, dadurch gekennzeichnet, daß es sich bei dem Metallsalz um ein Cobalt (II)- oder Cobalt(III)-Salz, ein Nickelsalz oder ein Gemisch daraus handelt.
EP94400090A 1993-06-29 1994-01-14 Gegen Einwirkung chemischer Verbindungen fälschungssicheres Blatt und daraus hergestelltes fälschungssicheres Dokument Expired - Lifetime EP0632162B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9307885A FR2694772B1 (fr) 1992-07-15 1993-06-29 Feuille infalsifiable par agent chimique et document de securite obtenu.
FR9307885 1993-06-29

Publications (2)

Publication Number Publication Date
EP0632162A1 EP0632162A1 (de) 1995-01-04
EP0632162B1 true EP0632162B1 (de) 1999-12-08

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Application Number Title Priority Date Filing Date
EP94400090A Expired - Lifetime EP0632162B1 (de) 1993-06-29 1994-01-14 Gegen Einwirkung chemischer Verbindungen fälschungssicheres Blatt und daraus hergestelltes fälschungssicheres Dokument

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EP (1) EP0632162B1 (de)
DE (1) DE69421965T2 (de)
ES (1) ES2142386T3 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU6697198A (en) * 1997-03-14 1998-10-12 Georgia-Pacific Corporation Security paper
FR2970716B1 (fr) 2011-01-25 2013-09-06 Honnorat Rech S & Services Papier de securite infalsifiable aux solvants

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0378029A2 (de) * 1988-12-07 1990-07-18 Aussedat-Rey Nichtfluoreszierendes, nichtfälschbares Sicherheitspapier und erhaltenes Dokument

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE635442C (de) * 1934-03-21 1936-09-17 Papierfabrik Spechthausen Akt Verfahren zur Herstellung von Sicherheitspapier
FR2693749A1 (fr) * 1992-07-15 1994-01-21 Arjo Wiggins Sa Feuille infalsifiable par agent chimique et document de sécurité obtenu.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0378029A2 (de) * 1988-12-07 1990-07-18 Aussedat-Rey Nichtfluoreszierendes, nichtfälschbares Sicherheitspapier und erhaltenes Dokument

Also Published As

Publication number Publication date
ES2142386T3 (es) 2000-04-16
DE69421965D1 (de) 2000-01-13
DE69421965T2 (de) 2000-06-29
EP0632162A1 (de) 1995-01-04

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