EP0632162A1 - Durch chemische Verbindungen fälscherungssicheres Blatt, und hergestelltes Sicherheitsdokument - Google Patents

Durch chemische Verbindungen fälscherungssicheres Blatt, und hergestelltes Sicherheitsdokument Download PDF

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Publication number
EP0632162A1
EP0632162A1 EP94400090A EP94400090A EP0632162A1 EP 0632162 A1 EP0632162 A1 EP 0632162A1 EP 94400090 A EP94400090 A EP 94400090A EP 94400090 A EP94400090 A EP 94400090A EP 0632162 A1 EP0632162 A1 EP 0632162A1
Authority
EP
European Patent Office
Prior art keywords
acid
sheet according
chosen
acids
sheet
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.)
Granted
Application number
EP94400090A
Other languages
English (en)
French (fr)
Other versions
EP0632162B1 (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 sheet which cannot be forged by chemical agents and also to the security document obtained. It relates more particularly to the field of security papers which can be used in particular for the production of payment documents or official documents such as bank checks, traveller's checks, books of accounting entries, titles, notarial acts, transport documents, and generally all documents for which it is essential to guard against any chemical falsification of the writings or seals carried on these said documents.
  • Papers are already known which contain reagents which develop a colored reaction under the action of certain chemical agents used to falsify inscriptions by chemical discoloration of the inks.
  • the object of the invention is to provide a safety sheet containing a metal salt as a chemical falsifying agent, the sensitivity of this salt towards falsifying agents being improved, that is to say that the reactions colored will be more intense than with salt alone or that 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 falsification chemical agents while using the smallest number of falsification reagents possible.
  • the metal salt is combined with a co-reactant chosen from the group formed by organic acids or their salts, organic acid derivatives, compounds having an aldehyde reducing function, compounds having a reducing function ketone, precursors of carbon dioxide.
  • the invention provides a sheet which cannot be forged by chemical agents, characterized in that it contains at least as an agent for forging a metal salt associated with a co-reactant chosen from the group formed by organic acids or their salts, organic acid, compounds having a reducing function aldehyde, compounds having a reducing function ketone, precursors of carbon dioxide.
  • the metal salt is chosen from cobalt II or III salts, nickel salts or their mixtures.
  • metal salts it is possible in particular to choose them from chlorides, sulfates, acetates, nitrates, these salts being anhydrous or hydrated.
  • an organic acid, its salt or a derivative makes it possible to obtain a colored reaction of great intensity in particular under the action of a saturated solution of sodium sulfite or under the action of sodium bisulfite or also under the action of redox couples such as the potassium permanganate / sodium bisulfite couple.
  • the organic acids are chosen from carboxylic acids or sulfonic acids.
  • the organic acid comprises at least two acid groups. These groups can be identical, for example the acid can only contain carboxylic groups, only sulfonic groups. These groups can also be different, for example the acid can contain groups that are both carboxylic (s) and sulfonic (s).
  • the carboxylic acid is chosen from the group formed by tartaric acid, phthalic acid, citric acid, malonic acid, tricarballylic acid, trimelittic acid.
  • the organic acid derivatives can be chosen from amides, lactams, esters, 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-sulfobenzoic anhydride.
  • the organic acid can be chosen from amino acids, and more particularly from glutamic acids or asparagines.
  • butyraldehyde Preferably used as compound having an aldehyde reducing function, butyraldehyde.
  • the carbon dioxide precursor is a carbonate or a bicarbonate, such as, for example, sodium carbonate or bicarbonate.
  • the unforgeable sheet is a paper with a purely cellulosic fibrous composition, partly synthetic or optionally purely synthetic.
  • the sheet may also be a plastic film, possibly coated.
  • the composition of the sheet may contain conventional agents used in stationery such as, for example, mineral fillers, 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 the tamper-evident sheet described above.
  • the wet take-up 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.
  • a plastic sheet is coated with this composition, the amount deposited dry being 10 g / m2.
  • the amount deposited dry being 10 g / m2.
  • 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). We treat a paper as in Example 2. Under the action of sulfite, an intense orange coloration is obtained, bisulfite an orange coloration, bleach. a brown coloring, sodium hydroxide a brown coloring, an ink eraser pencil an orange coloring, CORECTOR ink a pink to orange halo.

Landscapes

  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Paper (AREA)
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
FR9307885 1993-06-29
FR9307885A FR2694772B1 (fr) 1992-07-15 1993-06-29 Feuille infalsifiable par agent chimique et document de securite obtenu.

Publications (2)

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

Family

ID=9448659

Family Applications (1)

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

Country Status (3)

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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998041688A1 (en) * 1997-03-14 1998-09-24 Georgia-Pacific Corporation, Inc. Security paper
WO2012101334A1 (fr) 2011-01-25 2012-08-02 Honnorat Recherches & Services Papier infalsifiable aux solvants

Citations (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.

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2639970B1 (fr) * 1988-12-07 1991-09-20 Aussedat Rey Papier de securite infalsifiable, non fluorescent et document obtenu

Patent Citations (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.

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998041688A1 (en) * 1997-03-14 1998-09-24 Georgia-Pacific Corporation, Inc. Security paper
US6159585A (en) * 1997-03-14 2000-12-12 Georgia-Pacific Corporation Security paper
WO2012101334A1 (fr) 2011-01-25 2012-08-02 Honnorat Recherches & Services Papier infalsifiable aux solvants
US9057159B2 (en) 2011-01-25 2015-06-16 Honnorat Recherches & Services Paper that cannot be forged using solvents

Also Published As

Publication number Publication date
DE69421965D1 (de) 2000-01-13
EP0632162B1 (de) 1999-12-08
DE69421965T2 (de) 2000-06-29
ES2142386T3 (es) 2000-04-16

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