EP0190087B1 - Nicht zu fälschendes Sicherheitspapier, Verfahren zur Fälschungssicherung eines Papiers und wässrige oder organische Zusammensetzung, die insbesondere zur Fälschungssicherung eines Papiers nützlich ist - Google Patents

Nicht zu fälschendes Sicherheitspapier, Verfahren zur Fälschungssicherung eines Papiers und wässrige oder organische Zusammensetzung, die insbesondere zur Fälschungssicherung eines Papiers nützlich ist Download PDF

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Publication number
EP0190087B1
EP0190087B1 EP86420015A EP86420015A EP0190087B1 EP 0190087 B1 EP0190087 B1 EP 0190087B1 EP 86420015 A EP86420015 A EP 86420015A EP 86420015 A EP86420015 A EP 86420015A EP 0190087 B1 EP0190087 B1 EP 0190087B1
Authority
EP
European Patent Office
Prior art keywords
paper
compound
formula
forge
proof
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
EP86420015A
Other languages
English (en)
French (fr)
Other versions
EP0190087A1 (de
Inventor
André Honnorat
Claude Riou
Louis Raux
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.)
LANA MANUFACTURE DE PAPIER
International Paper SA
Original Assignee
Aussedat Rey 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 Aussedat Rey SA filed Critical Aussedat Rey SA
Publication of EP0190087A1 publication Critical patent/EP0190087A1/de
Application granted granted Critical
Publication of EP0190087B1 publication Critical patent/EP0190087B1/de
Expired legal-status Critical Current

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Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H21/00Non-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
    • D21H21/14Non-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
    • D21H21/40Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/46Elements suited for chemical verification or impeding chemical tampering, e.g. by use of eradicators
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/914Transfer or decalcomania
    • Y10S428/915Fraud or tamper detecting
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/27Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31971Of carbohydrate
    • Y10T428/31993Of paper

Definitions

  • the invention relates to the field of stationery. It relates to a new tamper-proof security paper comprising an aromatic product, a process for rendering a paper to be tamper-proof and an aqueous or organic composition useful, in particular, for rendering a tamper-proof paper.
  • French Patent No. 2,365,656 describes a security paper comprising a chemical sensitizing composition based on an indicator of acid-basicity, very sensitive to variations in pH.
  • the indicator is chosen, in particular, from the group of phthalein or sulfophthalein.
  • the pH rises due to the action of the eraser
  • the paper develops a color.
  • all of the products described are of delicate papermaking use, mainly because of their solubilization conditions, pH of use or reversibility or stability.
  • French Patent No. 2,399,505 and its certificate of addition 2,402,739 describe a security paper comprising a chemical sensitizing composition based on a salt of oxypyrene tricarboxylic acid, called Pyranine.
  • Pyranine a salt of oxypyrene tricarboxylic acid
  • French patents no. 2 406 027, 2 427 426 and its certificate of addition 2 432 576 describe a security paper comprising dinitrophenols which, under the action of an erasing pencil, are colored in non-fluorescent yellow.
  • French Patent No. 2,410,702 describes a security paper comprising a chemical sensitizing composition composed of Pyranin combined with an optical brightener and various other compounds. The action of an erasing felt on such a paper leads to a fluorescent yellow coloring.
  • the object of the invention is to provide a compound which, associated with a paper, makes it unforgeable, even with erasers, by instantly developing a color clearly detectable with the naked eye.
  • the paper according to the invention is characterized in that it comprises, on its surface and / or in its mass, at least one compound corresponding to the formula:
  • the paper can have any fibrous constitution, purely cellulosic or partly synthetic, to which can be added the conventional stationery additives, namely mineral fillers, various resistance agents, binders, resins, shading dyes, neutral bonding products, acid or basic, alumina sulfate for acid bonding or pH adjustment.
  • the conventional stationery additives namely mineral fillers, various resistance agents, binders, resins, shading dyes, neutral bonding products, acid or basic, alumina sulfate for acid bonding or pH adjustment.
  • N0 2 can be in ortho, meta or para of CH 2 CN.
  • the paper will comprise at least 0.0001 g / m 2 of the compound and, advantageously, between 0.01 and 0.15 g / m2.
  • the paper can also include sensitizing reagents, similar to those already used currently in security papers, for example products ensuring a modification of the appearance of the paper by contact of the latter with acids, oxidizing reagents.
  • sensitizing reagents similar to those already used currently in security papers, for example products ensuring a modification of the appearance of the paper by contact of the latter with acids, oxidizing reagents.
  • these products are introduced, either in aqueous solution, in which case it is necessary to ensure their retention on the fibers by direct bonding or by means of fixing agents, or in the microdispersed or pigmented precipitated state. .
  • ferric chloride / manganese ferrocyanide couple provides a reaction to attempts at falsification by acids, oxidants and erasers with an acid reaction (of the "corector" type).
  • These papers may also contain, in their mass, in the pigmented state, dispersed, one or more dyes insoluble in water but organo-soluble, so as to preserve the writings or statements made on these papers vis-à-vis attempts at falsification using organic solvents.
  • these papers can be watermarked or contain various devices intended to ensure recognition, such as fibers, pellets, colored and / or fluorescent particles.
  • a first method for making a falsifiable paper consists of incorporating the compound of formula (1) during the manufacture of the paper.
  • a second method consists in depositing on one or both sides of a sheet of paper an aqueous composition comprising a compound of formula (1), as defined above, and a coating binder.
  • coating binders mention may be made, by way of indication, of synthetic or natural polymers with compatible hydroxy terminations, such as starch, polyvinyl alcohol and cellulose derivatives.
  • the category of surfactant selected will depend on the structure of the compound corresponding to formula (I) used. Thus, for the substructure compounds (1), a surfactant from category (B) will advantageously be chosen and, for the substructure compounds (2), a surfactant from group (C) and, among these, the quaternary ammonium compounds.
  • chlorine activators such as bleach can be added to this composition.
  • a third method consists in depositing on one or both sides of a sheet of paper a composition comprising a compound of formula (1), an organic solvent and a compatible coating binder.
  • solvent there may be mentioned esters, ketones, alcohols, essences or aromatics.
  • composition designates solutions, that is to say the compositions in which the constituents are in the form of solutes but, also, the dispersions partially or not dissolved.
  • compositions can be deposited using a coating technique used in stationery (for example size press, roller systems, blade.
  • a subject of the invention is also the compositions as such.
  • the coloring obtained with ink erasers and bases is purple-magenta.
  • the paper thus treated also reacts with bleach, giving a beige-brown color, with acids and acid-erasing products (of the "corector” type), producing blue, the solvents color differently the paper according to their nature.
  • reaction with acids, bleach and acid reaction erasers can be obtained by addition of products usually known in the coating solution or in the bulk.
  • the paper thus treated becomes purple-magenta in the presence of bases, reducers or erasable felts, and. as before, in blue with the acids and the acid-erasing products with acid reaction (of the "corector” type), in brown with the bleach and of a variable coloring according to the solvents (according to the dye used).
  • a paper support During the manufacture of a paper support, are introduced into the mass, in addition to the reagents previously described as a ferric salt, a precipitate of manganese ferrocyanide and one or more dispersed organosoluble dyes, paranitrophenyl acetonitrile: finely divided, in combination with hexadecyl pyridinium chloride. After formation of the sheet, a reactivity identical to that described in Example 1 is obtained (magenta coloring with erasers, bases and reducers, blue with acids and erasers with acid reaction (of the "corector” type). ), brown with bleach, variable with solvents).
  • the paper is white and not fluorescent after facing.

Landscapes

  • Paper (AREA)
  • Color Printing (AREA)

Claims (15)

1. Nicht zu fälschendes Sicherheitspapier,
dadurch gekennzeichnet, daß es auf der Oberfläche und/oder in der Masse mindestens eine Verbindung der Formel (I) enthält:
Figure imgb0029
in der bedeuten:
-R Wasserstoff, ggfs. substituiertes C1-8-Alkyl, nicht substituiertes Amin, N-substituiertes oder N,N-disubstituiertes Amin, N02 oder Halogen,
-n 0 oder 1.
2. Sicherheitspapier nach Anspruch 1, dadurch gekennzeichnet, daß die Verbindung der Formel (I) die folgende Struktur hat:
Figure imgb0030
in der RH, ggfs substituiertes Alkyl, NH2, NHR', NR'R" (wobei R' und R" verschiedene Arylgruppen, die insbesondere durch CN und/oder N02 substituiert sind, oder Alkylgruppen sein können), Halogen oder NO2 bedeutet.
3. Sicherheitspapier nach Anspruch 1, dadurch gekennzeichnet, daß die Verbindung der Formel (I) die folgende Struktur hat:
Figure imgb0031
4. Sicherheitspapier nach Anspruch 2, dadurch gekennzeichnet, daß die Verbindung unter folgenden Verbindungen ausgewählt wird:
- m-Benzonitril
Figure imgb0032
- 2-Amino-5-nitrobenzonitril
Figure imgb0033
- 3,5-Dinitrobenzonitril
Figure imgb0034
- 2-Chlor-5-nitrobenzonitril
Figure imgb0035
- N,N-Di(2-cyano-4-nitrophenyl)-amin
Figure imgb0036
5. Sicherheitspapier nach Anspruch 3, dadurch gekennzeichnet, daß die Verbindung unter folgenden Verbindungen ausgewählt wird:
- o-Nitrophenylacetonitril
Figure imgb0037
- p-Nitrophenylacetonitril
Figure imgb0038
6. Sicherheitspapier nach Anspruch 1, dadurch gekennzeichnet, daß das Papier mindestens 0,0001 g/m2 der Verbindung der Formel (1) enthält.
7. Verfahren zur Fälschungssicherung eines Papiers, dadurch gekennzeichnet, daß dem Papier mindestens eine Verbindung nach den Ansprüchen 1-5 zugegeben wird.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß die Verbindung dem Papier während seiner Herstellung zugegeben wird.
9. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß auf eine oder beide Seiten eines Papierblattes eine wäßrige Zusammensetzung aufgebracht wird, die eine Verbindung der Formel (I) nach einem der Ansprüche 1-5 und ein Streichbindemittel enthält.
10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß die Zusammensetzung außerdem ein grenzflächenaktives Mittel enthält.
11. Verfahren nach Anspruch 9 oder 10, dadurch gekennzeichnet, daß die Zusammensetzung in g/I enthält:
-0,5 bis 50 g der Verbindung der Formel (I), allein oder als Gemisch,
- 10 bis 150 g Streichbindemittel,
- 5 bis 50 g grenzflächenaktives Mittel und
-1 bis 100 g andere Hilfsmittel, beispielsweise Aktivatoren.
12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß die Verbindung die im Anspruch 2 angegebene Formel hat und das grenzflächenaktive Mittel neutral ist.
13. Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß die Verbindung die im Anspruch 3 angegebene Formel hat und das grenzflächenaktive Mittel kationisch ist.
14. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß auf eine oder beide Seiten eines Papierblattes eine organische Zusammensetzung mit der Verbindung der Formel (I) und einem verträglichem Streichbindemittels aufgebracht wird.
15. Wäßrige oder organische Zusammensetzung nach einem der Ansprüche 9, 10, 11, 12, 13 und 14 zur Verwendung insbesondere bei der Fälschungssicherung eines Sicherheitspapiers.
EP86420015A 1985-01-21 1986-01-16 Nicht zu fälschendes Sicherheitspapier, Verfahren zur Fälschungssicherung eines Papiers und wässrige oder organische Zusammensetzung, die insbesondere zur Fälschungssicherung eines Papiers nützlich ist Expired EP0190087B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8500939 1985-01-21
FR8500939A FR2576332B1 (fr) 1985-01-21 1985-01-21 Papier de securite infalsifiable, procede pour rendre infalsifiable un papier et composition aqueuse ou organique utile, notamment, pour rendre un papier infalsifiable

Publications (2)

Publication Number Publication Date
EP0190087A1 EP0190087A1 (de) 1986-08-06
EP0190087B1 true EP0190087B1 (de) 1988-04-06

Family

ID=9315534

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86420015A Expired EP0190087B1 (de) 1985-01-21 1986-01-16 Nicht zu fälschendes Sicherheitspapier, Verfahren zur Fälschungssicherung eines Papiers und wässrige oder organische Zusammensetzung, die insbesondere zur Fälschungssicherung eines Papiers nützlich ist

Country Status (6)

Country Link
US (1) US4725497A (de)
EP (1) EP0190087B1 (de)
CA (1) CA1276414C (de)
DE (1) DE3660121D1 (de)
FR (1) FR2576332B1 (de)
PT (1) PT81877B (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2647820B1 (fr) * 1989-06-01 1991-09-20 Aussedat Rey Papier de securite infalsifiable et composition aqueuse ou organique utile, notamment pour rendre un papier infalsifiable
FR2654445B1 (fr) * 1989-11-14 1995-04-28 Arjomari Prioux Papier de securite comportant un nouveau fil de securite reagissant a la falsification.
US5209515A (en) * 1991-02-08 1993-05-11 The Standard Register Company Solvent and/or pressure sensitive security document
US5718456A (en) * 1994-01-26 1998-02-17 Michael F. Detwiler, Jr. Method for verifying authenticity of sales record
DE19510974A1 (de) * 1995-03-24 1996-09-26 Drescher Geschaeftsdrucke Einlagiges Papiererzeugnis
US6783991B1 (en) 2002-02-06 2004-08-31 The Standard Register Company Reversible and reusable authentication system for secure documents
DE102007006059A1 (de) * 2007-02-02 2008-08-07 Peter Dr. Schneider Verfahren zum Schutz von Produkten und Dokumenten auf Thermopapierbasis gegen Manipulation
FR2970716B1 (fr) 2011-01-25 2013-09-06 Honnorat Rech S & Services Papier de securite infalsifiable aux solvants
FR2978461A1 (fr) * 2011-07-29 2013-02-01 Arjowiggins Security Substrat de securite et methode d'authentification et de mise en evidence des tentatives de falsification
FR2981955B1 (fr) 2011-10-26 2013-11-01 Honnorat Rech S & Services Papier de securite infalsifiable aux agents oxydo-reducteurs

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2333979A (en) * 1941-08-15 1943-11-09 Fox River Paper Corp Safety paper
US3162675A (en) * 1961-09-19 1964-12-22 Dow Chemical Co Process for making nitroaromatic nitriles
GB1435686A (en) * 1972-04-26 1976-05-12 Culter Guard Bridge Holdings L Coated paper
FR2406027A1 (fr) * 1977-10-14 1979-05-11 Voiron Papeteries Papier reagissant a la falsification par agents chimiques et son procede de fabrication
JPS54115907A (en) * 1977-12-02 1979-09-08 Barry Graham Charles Thin sheet printed with transparent ink* and developer eraser for said ink
JPH0212197B2 (de) * 1980-05-30 1990-03-19 Gee Aa Oo G Fuyuuru Automatsuioon Unto Oruganizatsuioon Mbh

Also Published As

Publication number Publication date
DE3660121D1 (en) 1988-05-11
PT81877A (fr) 1986-02-01
FR2576332A1 (fr) 1986-07-25
CA1276414C (en) 1990-11-20
FR2576332B1 (fr) 1987-04-10
US4725497A (en) 1988-02-16
EP0190087A1 (de) 1986-08-06
PT81877B (pt) 1987-11-30

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