EP0494828A1 - Safety document - Google Patents

Safety document Download PDF

Info

Publication number
EP0494828A1
EP0494828A1 EP92400058A EP92400058A EP0494828A1 EP 0494828 A1 EP0494828 A1 EP 0494828A1 EP 92400058 A EP92400058 A EP 92400058A EP 92400058 A EP92400058 A EP 92400058A EP 0494828 A1 EP0494828 A1 EP 0494828A1
Authority
EP
European Patent Office
Prior art keywords
alkalinity
document
sodium sulfite
aldehyde
agent
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
EP92400058A
Other languages
German (de)
French (fr)
Other versions
EP0494828B1 (en
Inventor
Michel Camus
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
Application filed by ArjoWiggins SAS filed Critical ArjoWiggins SAS
Publication of EP0494828A1 publication Critical patent/EP0494828A1/en
Application granted granted Critical
Publication of EP0494828B1 publication Critical patent/EP0494828B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03Non-macromolecular organic compounds
    • D21H17/05Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/06Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
    • 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

Definitions

  • the invention relates to a security document which cannot be forged by a chemical agent, in particular by sodium sulfite.
  • Such documents can be used as bank checks, traveller's checks, titles, notarial acts, etc ... for which it is essential to guard against any chemical falsification of the writings or seals carried on these documents.
  • the ink erasing pencils contain sodium sulfite in an alkaline medium, their pH is of the order of 10.
  • This alkaline character is used to reveal the falsification by incorporating in mass or on the surface of the document a colored indicator which turns well visibly at a pH of 9.5-10.
  • a clearly visible coloration is obtained at a pH of 9.5-10, red with phenolphthalein as described in patent FR-A-2,365,656; a blue coloration is obtained with the AS check dye sold by the company BASF.
  • the object of the invention is to provide a security document which cannot be forged by sodium sulfite in particular and which comprises at least one agent sensitive to bases, this agent betraying adulteration with sulfite and which can be chosen from a wide range of compounds in order to to be able to choose a color revealing the falsification which is well contrasted with the color of the final document.
  • the object of the invention can be achieved by incorporating in mass and / or on the surface of the document, at least one alkalinity-generating compound under the action of a saturated solution of sodium sulfite. This compound then increases the pH of the document during the falsification attempt and there follows a colored reaction with the agent sensitive to the bases.
  • the base-sensitive agent may be a colored indicator or a strong base-sensitive agent such as, for example, manganese chloride.
  • R can be any, a carbon chain, saturated or not, linear or branched, contain heteroatoms, one or more rings, heterocycles, aromatic rings.
  • Dialdehydes rather than monoaldehydes are preferably used because they generate twice as much alkalinity.
  • alkalinity-generating compounds indirectly comprising at least one aldehyde function or at least one ketone function. These compounds are considered to be alkalinity generators according to the invention.
  • these may be compounds commonly used as microbicides and which generate formaldehyde; in particular, they may be compounds comprising the methylol group -CH2OH such as hemiformals, sulfur compounds S-methylol or nitrogen compounds N-methylol.
  • the invention therefore more particularly provides a document which is characterized in that the alkalinity generator is a compound comprising directly or indirectly at least one aldehyde function or at least one ketone function.
  • non-volatile compounds and / or compounds having substantial properties towards the material (for example cellulose) constituting the document to be secured are selected.
  • the compounds which have no unpleasant odor and which are well soluble in water are chosen so that their use is simple and to avoid the problems associated with organic solvents (toxicity, risks of explosion. ..).
  • aldehyde salycilic aldehyde or a dialdehyde such as glutaric aldehyde can be used in particular.
  • These aldehydes are perfectly compatible with the other solvent-reactive infalsification agents, redox agents such as that described in the patent of the Applicant FRA-2,580,303, with chlorinated products (bleach).
  • the invention more particularly provides a document containing by mass as a colored indicator the dye for check AS sold by BASF and comprising on the surface of glutaraldehyde and such that it develops a blue coloration under the action of a saturated aqueous solution. in sodium sulfite.
  • the invention more particularly provides a document comprising on the surface as a colored indicator of phenolphthalein and also comprising on the surface of glutaraldehyde and such that it develops a red coloration under the action of an aqueous solution saturated with sodium sulfite .
  • the invention more particularly provides a document comprising on the surface as an agent sensitive to strong bases of manganese chloride and comprising on the surface of glutaraldehyde and such that it develops a brown coloration under the action of a saturated aqueous solution in sodium sulfite.
  • the security document according to the invention can in particular be obtained by the papermaking route from a purely cellulosic fibrous composition or containing synthetic fibers, and optionally containing mineral fillers, dyes and other adjuvants usually used in stationery.
  • the document may therefore include other agents reactive to chemical tampering compatible with the alkalinity generator; it can also include physical authentication agents such as watermarks, security threads, boards, fluorescent fibers, iridescent pigments, etc.
  • the alkalinity-generating compound can be incorporated en masse during the production of the document. It can also be placed on the surface of the document by coating, printing or impregnating with a size press of the document with a composition containing said compound and a binder and optionally the agent sensitive to bases.
  • the quantities of alkalinity-generating compounds and of agents sensitive to the bases will be adjusted by the skilled person according to the intensity of the desired coloring, according to the sensitivity of the compounds and agent reactive to the bases, and also so as not to significantly change the color of the document.
  • a sheet is produced by the papermaking route from a cellulosic fibrous composition and possibly other adjuvants.
  • This sheet is dried.
  • a sheet is produced by the papermaking route from a cellulosic fibrous composition and possibly other adjuvants.
  • This sheet is dried.
  • the whiteness is 70-85 photovolts.
  • a sheet is produced by the papermaking route from a cellulosic fibrous composition to which 0.02 to 0.5% is added on a dry basis relative to the fibrous composition of a colored indicator, the dye for check AS marketed by BASF, and possibly other adjuvants.
  • the quantity deposited is approximately 40 g / m2 in dry.
  • This sheet is dried.
  • a sheet is produced by the papermaking route from a cellulosic fibrous composition and possibly other adjuvants.
  • This sheet is dried.
  • a sheet is produced by the papermaking route from a cellulosic fibrous composition and possibly other adjuvants.
  • This sheet is dried.
  • a sheet is produced by the papermaking route from a cellulosic fibrous composition and possibly other adjuvants.
  • This sheet is dried.

Abstract

Security document which cannot be falsified with a chemical agent, especially with sodium sulphite, comprising at least one agent which is sensitive to bases, characterised in that it comprises at the surface and/or in bulk at least one compound generating alkalinity under the action of sodium sulphite. The alkalinity generator is preferably an aldehyde or a ketone. The invention is also intended to provide a composition intended to make a document incapable of being falsified with sodium sulphite, whose characteristic is that it contains: - at least one compound generating alkalinity< - at least one agent sensitive to strong bases and/or a coloured indicator - at least one binder usually employed in paper manufacture. e

Description

L'invention concerne un document de sécurité infalsifiable par agent chimique, notamment par le sulfite de sodium.The invention relates to a security document which cannot be forged by a chemical agent, in particular by sodium sulfite.

De tels documents peuvent être utilisés comme chèques bancaires, chèques de voyage, titres, actes notariés, etc... pour lesquels il est indispensable de se prémunir contre toute falsification chimique des écritures ou cachets portés sur ces documents.Such documents can be used as bank checks, traveller's checks, titles, notarial acts, etc ... for which it is essential to guard against any chemical falsification of the writings or seals carried on these documents.

Des documents infalsifiables par les crayons effaceurs ont été décrits par exemple dans les brevets FR-A-2 365 656, FR-A-2 399 505 et son certificat d'addition FR-E-2 402 739 de la demanderesse.Documents which cannot be forged by erasers are described, for example, in patents FR-A-2,365,656, FR-A-2,399,505 and its certificate of addition FR-E-2,402,739 to the applicant.

Les crayons effaceurs d'encre contiennent du sulfite de sodium en milieu alcalin, leur pH est de l'ordre de 10. On utilise ce caractère alcalin pour révéler la falsification en incorporant en masse ou à la surface du document un indicateur coloré qui vire bien visiblement à un pH de 9,5-10. Par exemple, on obtient une coloration bien visible à un pH de 9,5-10, en rouge avec la phénolphtaléine comme décrit dans le brevet FR-A-2 365 656; on obtient une coloration bleue avec le colorant pour chèque AS vendu par la société BASF.The ink erasing pencils contain sodium sulfite in an alkaline medium, their pH is of the order of 10. This alkaline character is used to reveal the falsification by incorporating in mass or on the surface of the document a colored indicator which turns well visibly at a pH of 9.5-10. For example, a clearly visible coloration is obtained at a pH of 9.5-10, red with phenolphthalein as described in patent FR-A-2,365,656; a blue coloration is obtained with the AS check dye sold by the company BASF.

Cependant si l'on tente d'effacer une écriture portée par exemple avec une encre pour stylo plume en utilisant une solution aqueuse saturée en sulfite de sodium, la falsification n'est pas révélée avec les indicateurs colorés précédents. En effet, une telle solution saturée a un pH de 9, donc un pH inférieur à celui donnant un virage bien visible de l'indicateur coloré.However, if an attempt is made to erase a writing worn for example with an ink for a fountain pen using an aqueous solution saturated with sodium sulfite, the falsification is not revealed with the preceding colored indicators. Indeed, such a saturated solution has a pH of 9, therefore a pH lower than that giving a clearly visible shift in the colored indicator.

Dans la demande de brevet FR-A-2 647 820, on a décrit des documents de sécurité infalsifiables contenant des produits comme le rutin trihydrate ou le narigin hydrate qui donnent une réaction jaune avec les crayons effaceurs ou les bases, de la 1,8 dihydroxyanthraquinone qui donne une réaction orangé-rouge avec les crayons effaceurs et rouge avec les bases; le pH permettant d'avoir une coloration bien visible n'est pas précisé. Un inconvénient de cette invention est son emploi de produits très particuliers.In patent application FR-A-2 647 820, tamper-resistant security documents have been described containing products such as rutin trihydrate or narigin hydrate which give a yellow reaction with erasers or bases, from 1.8 dihydroxyanthraquinone which gives an orange-red reaction with the erasers and red with the bases; the pH allowing a clearly visible coloration is not specified. A disadvantage of this invention is its use of very specific products.

Dans les brevets FR-A-2 406 027, FR-A-2 427 426 et le certificat d'addition FR-E-2 432 576 on a décrit des documents de sécurité infalsifiables par agent chimique et contenant des nitrophénols. Le paranitrophénol a une zone de virage suffisamment large pour réagir à la fois au crayon effaceur et à une solution saturée en sulfite de sodium en développant une coloration jaune. Il sera cependant difficile d'observer une telle couleur si le document a pour couleur de fond le jaune ou une couleur peu contrastante avec le jaune.In patents FR-A-2 406 027, FR-A-2 427 426 and the certificate of addition FR-E-2 432 576, security documents which cannot be forged by agent have been described. chemical and containing nitrophenols. Paranitrophenol has a sufficiently wide turning zone to react both with the eraser pencil and with a saturated solution of sodium sulfite, developing a yellow coloration. However, it will be difficult to observe such a color if the document has a background color of yellow or a color that has little contrast with yellow.

Le but de l'invention est de fournir un document de sécurité infalsifiable en particulier par le sulfite de sodium et comportant au moins un agent sensible aux bases, cet agent trahissant la falsification par le sulfite et pouvant être choisi parmi une large gamme de composés afin de pouvoir choisir une coloration révélatrice de la falsification qui soit bien contrastée avec la couleur du document final.The object of the invention is to provide a security document which cannot be forged by sodium sulfite in particular and which comprises at least one agent sensitive to bases, this agent betraying adulteration with sulfite and which can be chosen from a wide range of compounds in order to to be able to choose a color revealing the falsification which is well contrasted with the color of the final document.

La demanderesse a découvert que le but de l'invention peut être atteint en incorporant en masse et/ou à la surface du document, au moins un composé générateur d'alcalinité sous l'action d'une solution saturée en sulfite de sodium. Ce composé augmente alors le pH du document lors de la tentative de falsification et il s'ensuit une réaction colorée avec l'agent sensible aux bases.The Applicant has discovered that the object of the invention can be achieved by incorporating in mass and / or on the surface of the document, at least one alkalinity-generating compound under the action of a saturated solution of sodium sulfite. This compound then increases the pH of the document during the falsification attempt and there follows a colored reaction with the agent sensitive to the bases.

L'agent sensible aux bases peut être un indicateur coloré ou un agent sensible aux bases fortes comme par exemple le chlorure de manganèse.The base-sensitive agent may be a colored indicator or a strong base-sensitive agent such as, for example, manganese chloride.

Comme composés générateurs d'alcalinité sous l'action d'une solution saturée en sulfite de sodium, on utilise plus particulièrement les composés comportant au moins une fonction aldéhyde.As compounds which generate alkalinity under the action of a saturated solution of sodium sulfite, use is more particularly made of compounds comprising at least one aldehyde function.

En effet ces composés libèrent de l'hydroxyde de sodium en milieu aqueux selon le schéma réactionnel suivant: R-COH + H₂O + Na₂SO₃ ----> NaOH + R-CH(SO₃Na)OH

Figure imgb0001
In fact, these compounds release sodium hydroxide in an aqueous medium according to the following reaction scheme: R-COH + H₂O + Na₂SO₃ ----> NaOH + R-CH (SO₃Na) OH
Figure imgb0001

R peut être quelconque, une chaîne carbonée, saturée ou non, linéaire ou ramifiée, comporter des hétéroatomes, un ou plusieurs cycles, hétérocycles, noyaux aromatiques.R can be any, a carbon chain, saturated or not, linear or branched, contain heteroatoms, one or more rings, heterocycles, aromatic rings.

On utilise de préférence les dialdéhydes aux monoaldéhydes car ils génèrent deux fois plus d'alcalinité.Dialdehydes rather than monoaldehydes are preferably used because they generate twice as much alkalinity.

Comme autres composés générateurs d'alcalinité sous l'action d'une solution saturée en sulfite de sodium, on peut utiliser les composés comportant au moins une fonction cétone.As other compounds which generate alkalinity under the action of a saturated solution of sodium sulfite, it is possible to use the compounds comprising at least one ketone function.

Des essais faits par la Demanderesse ont montré que les cétones ayant une chaine carbonée linéaire et ayant au plus cinq carbone donnent les meilleurs résultats.Tests carried out by the Applicant have shown that ketones having a linear carbon chain and having at most five carbon give the best results.

On peut également utiliser des composés générateurs d'alcalinité comportant indirectement au moins une fonction aldéhyde ou au moins une fonction cétone. Ces composés sont considérés comme des générateurs d'alcalinité conformément à l'invention.It is also possible to use alkalinity-generating compounds indirectly comprising at least one aldehyde function or at least one ketone function. These compounds are considered to be alkalinity generators according to the invention.

Par exemple, il peut s'agir de composés utilisés habituellement comme microbicides et qui génèrent du formaldéhyde; en particulier il peut s'agir de composés comportant le groupement méthylol -CH₂OH comme les hémiformals, les composés soufrés S-méthylol ou les composés azotés N-méthylol.For example, these may be compounds commonly used as microbicides and which generate formaldehyde; in particular, they may be compounds comprising the methylol group -CH₂OH such as hemiformals, sulfur compounds S-methylol or nitrogen compounds N-methylol.

L'invention fournit donc plus particulièrement un document qui se caractérise par le fait que le générateur d'alcalinité est un composé comportant directement ou indirectement au moins une fonction aldéhyde ou au moins une fonction cétone.The invention therefore more particularly provides a document which is characterized in that the alkalinity generator is a compound comprising directly or indirectly at least one aldehyde function or at least one ketone function.

On sélectionne de préférence des composés non volatils et/ou présentant des propriétés de substantivité envers la matière (par exemple la cellulose) constituant le document à sécuriser.Preferably, non-volatile compounds and / or compounds having substantial properties towards the material (for example cellulose) constituting the document to be secured are selected.

On choisit de préférence les composés qui n'ont pas d'odeur désagréable et qui sont bien solubles dans l'eau afin que leur mise en oeuvre soit simple et d'éviter les problèmes liés aux solvants organiques (toxicité, risques d'explosion ...).Preferably, the compounds which have no unpleasant odor and which are well soluble in water are chosen so that their use is simple and to avoid the problems associated with organic solvents (toxicity, risks of explosion. ..).

L'homme du métier choisira ces composés de façon à ce qu'ils soient compatibles avec les autres agents d'infalsification chimique retenus.Those skilled in the art will choose these compounds so that they are compatible with the other selected chemical forging agents.

Comme aldéhyde on peut utiliser en particulier l'aldéhyde salycilique ou un dialdéhyde comme l'aldéhyde glutarique. Ces aldéhydes sont parfaitement compatibles avec les autres agents d'infalsification réactifs aux solvants, aux oxydo-réducteurs comme celui décrit dans le brevet de la Demanderesse FRA-2 580 303, aux produits chlorés (eau de javel).As aldehyde, salycilic aldehyde or a dialdehyde such as glutaric aldehyde can be used in particular. These aldehydes are perfectly compatible with the other solvent-reactive infalsification agents, redox agents such as that described in the patent of the Applicant FRA-2,580,303, with chlorinated products (bleach).

L'invention fournit plus particulièrement un document contenant en masse comme indicateur coloré le colorant pour chèque AS vendu par BASF et comportant en surface de l'aldéhyde glutarique et tel qu'il développe une coloration bleue sous l'action d'une solution aqueuse saturée en sulfite de sodium.The invention more particularly provides a document containing by mass as a colored indicator the dye for check AS sold by BASF and comprising on the surface of glutaraldehyde and such that it develops a blue coloration under the action of a saturated aqueous solution. in sodium sulfite.

L'invention fournit plus particulièrement un document comportant en surface comme indicateur coloré de la phénolphtaléine et comportant également en surface de l'aldéhyde glutarique et tel qu'il développe une coloration rouge sous l'action d'une solution aqueuse saturée en sulfite de sodium.The invention more particularly provides a document comprising on the surface as a colored indicator of phenolphthalein and also comprising on the surface of glutaraldehyde and such that it develops a red coloration under the action of an aqueous solution saturated with sodium sulfite .

L'invention fournit plus particulièrement un document comportant en surface comme agent sensible aux bases fortes du chlorure de manganèse et comportant en surface de l'aldéhyde glutarique et tel qu'il développe une coloration marron sous l'action d'une solution aqueuse saturée en sulfite de sodium.The invention more particularly provides a document comprising on the surface as an agent sensitive to strong bases of manganese chloride and comprising on the surface of glutaraldehyde and such that it develops a brown coloration under the action of a saturated aqueous solution in sodium sulfite.

Le document de sécurité selon l'invention peut être en particulier obtenu par voie papetière à partir d'une composition fibreuse purement cellulosique ou contenant des fibres synthétiques, et contenant éventuellement des charges minérales, des colorants et autres adjuvants utilisés habituellement en papeterie.The security document according to the invention can in particular be obtained by the papermaking route from a purely cellulosic fibrous composition or containing synthetic fibers, and optionally containing mineral fillers, dyes and other adjuvants usually used in stationery.

Le document peut donc comporter d'autres agents réactifs aux infalsifications chimiques compatibles avec le générateur d'alcalinité; il peut aussi comporter des agents physiques d'authentification comme les filigranes, fils de sécurité, planchettes, fibres fluorescentes, pigments iridescents etc... .The document may therefore include other agents reactive to chemical tampering compatible with the alkalinity generator; it can also include physical authentication agents such as watermarks, security threads, boards, fluorescent fibers, iridescent pigments, etc.

Le composé générateur d'alcalinité peut être incorporé en masse lors de la fabrication du document. Il peut aussi être mis à la surface du document en réalisant un couchage, une impression ou une imprégnation avec une presse encolleuse du document par une composition contenant ledit composé et un liant et éventuellement l'agent sensible aux bases.The alkalinity-generating compound can be incorporated en masse during the production of the document. It can also be placed on the surface of the document by coating, printing or impregnating with a size press of the document with a composition containing said compound and a binder and optionally the agent sensitive to bases.

Les quantités de composés générateurs d'alcalinité et d'agents sensibles aux bases seront réglées par l'Homme du métier selon l'intensité de la coloration souhaitée, selon la sensibilité des composés et agent réactif aux bases, et également de façon à ne pas altérer notablement la teinte du document.The quantities of alkalinity-generating compounds and of agents sensitive to the bases will be adjusted by the skilled person according to the intensity of the desired coloring, according to the sensitivity of the compounds and agent reactive to the bases, and also so as not to significantly change the color of the document.

L'invention vise aussi à fournir une composition destinée à rendre un document infalsifiable par le sulfite de sodium ayant pour caractéristique le fait qu'elle contient:

  • au moins un composé générateur d'alcalinité,
  • au moins un agent sensible aux bases fortes et/ou un indicateur coloré,
  • au moins un liant habituellement utilisé en papeterie.
The invention also aims to provide a composition intended to make a document unforgeable by sodium sulfite having the characteristic that it contains:
  • at least one alkalinity-generating compound,
  • at least one agent sensitive to strong bases and / or a colored indicator,
  • at least one binder usually used in stationery.

L' invention fournit en particulier une composition ayant pour caractéristique le fait qu'elle contient :

  • au moins un composé générateur d'alcalinité choisi parmi les composés comportant directement ou indirectement au moins une fonction aldéhyde ou au moins une fonction cétone,
  • au moins un agent sensible aux bases fortes et/ou un indicateur coloré,
  • au moins un liant habituellement utilisé en papeterie.
The invention provides in particular a composition having the characteristic that it contains:
  • at least one alkalinity-generating compound chosen from compounds comprising directly or indirectly at least one aldehyde function or at least one ketone function,
  • at least one agent sensitive to strong bases and / or a colored indicator,
  • at least one binder usually used in stationery.

Les exemples non limitatifs suivants permettront de mieux comprendre l'invention:The following nonlimiting examples will allow a better understanding of the invention:

EXEMPLE 1 comparatif : Comparative EXAMPLE 1 :

On réalise une feuille par voie papetière à partir d'une composition fibreuse cellulosique et éventuellement d'autres adjuvants.A sheet is produced by the papermaking route from a cellulosic fibrous composition and possibly other adjuvants.

On imprègne cette feuille avec une composition aqueuse contenant, en sec:

  • 2 à 15 parties d'un liant (amidon par exemple)
  • 0,05 à 2 parties d'un indicateur coloré ,la phénolphtaléine.
This sheet is impregnated with an aqueous composition containing, dry:
  • 2 to 15 parts of a binder (starch for example)
  • 0.05 to 2 parts of a colored indicator, phenolphthalein.

On sèche cette feuille.This sheet is dried.

Si on essaie de falsifier le document obtenu à l'aide d'un crayon effaceur, il se développe une coloration rouge.If you try to falsify the document obtained using an eraser, a red color develops.

Si on essaie de le falsifier avec une solution aqueuse saturée en sulfite de sodium, il ne se développe aucune coloration notable à l'oeil nu.If one tries to falsify it with a saturated aqueous solution of sodium sulfite, it does not develop any noticeable coloration with the naked eye.

EXEMPLE 2 : EXAMPLE 2 :

On réalise une feuille par voie papetière à partir d'une composition fibreuse cellulosique et éventuellement d'autres adjuvants.A sheet is produced by the papermaking route from a cellulosic fibrous composition and possibly other adjuvants.

On imprègne cette feuille avec une composition aqueuse contenant, en sec:

  • 2 à 15 parties d'un liant (amidon par exemple)
  • 0,05 à 2 parties d'un indicateur coloré ,la phénolphtaléine
  • 0,5 à 4 parties d'un composé générateur d'alcalinité ,l'aldéhyde glutarique .
This sheet is impregnated with an aqueous composition containing, dry:
  • 2 to 15 parts of a binder (starch for example)
  • 0.05 to 2 parts of a colored indicator, phenolphthalein
  • 0.5 to 4 parts of an alkalinity-generating compound, glutaric aldehyde.

On sèche cette feuille.This sheet is dried.

Si on essaie de falsifier le document obtenu à l'aide d'un crayon effaceur ,il se développe une coloration rouge.
Si on essaie de le falsifier avec une solution aqueuse saturée en sulfite de sodium, il se développe également une coloration rouge parfaitement visible à l'oeil nu.
If you try to falsify the document obtained using an eraser, a red color develops.
If we try to falsify it with a saturated aqueous solution of sodium sulfite, it also develops a red color that is perfectly visible to the naked eye.

De plus la teinte du papier n'est pas modifiée, la blancheur est de 70-85 photovolts.In addition the tint of the paper is not changed, the whiteness is 70-85 photovolts.

EXEMPLE 3 : EXAMPLE 3 :

On réalise une feuille par voie papetière à partir d'une composition fibreuse cellulosique à laquelle on ajoute 0,02 à 0,5 % en sec par rapport à la composition fibreuse d'un indicateur coloré, le colorant pour chèque AS commercialisé par BASF, et éventuellement d'autres adjuvants.A sheet is produced by the papermaking route from a cellulosic fibrous composition to which 0.02 to 0.5% is added on a dry basis relative to the fibrous composition of a colored indicator, the dye for check AS marketed by BASF, and possibly other adjuvants.

On imprègne cette feuille avec une composition aqueuse contenant, en sec:

  • 2 à 15 parties d'un liant (amidon par exemple)
  • 0,5 à 4 parties d'un composé générateur d'alcalinité ,l'aldéhyde glutarique.
This sheet is impregnated with an aqueous composition containing, dry:
  • 2 to 15 parts of a binder (starch for example)
  • 0.5 to 4 parts of an alkalinity-generating compound, glutaric aldehyde.

La quantité déposée est d'environ 40 g/m² en sec.The quantity deposited is approximately 40 g / m² in dry.

On sèche cette feuille.This sheet is dried.

Si on essaie de falsifier le document obtenu à l'aide d'un crayon effaceur, il se développe une coloration bleue.If you try to falsify the document obtained using an eraser, a blue color develops.

Si on essaie de le falsifier avec une solution aqueuse saturée en sulfite de sodium, il se développe également une coloration bleue parfaitement visible à l'oeil nu.If we try to falsify it with a saturated aqueous solution of sodium sulfite, it also develops a blue coloration perfectly visible to the naked eye.

EXEMPLE 4 : EXAMPLE 4 :

On réalise une feuille par voie papetière à partir d'une composition fibreuse cellulosique et éventuellement d'autres adjuvants.A sheet is produced by the papermaking route from a cellulosic fibrous composition and possibly other adjuvants.

On imprègne cette feuille avec une composition aqueuse contenant ,en sec

  • 2 à 15 parties d'un liant (amidon par exemple),
  • 0,05 à 4 parties d'un agent sensible aux bases, le chlorure de manganèse,
  • 0,5 à 4 parties d'un composé générateur d'alcalinité , l'aldéhyde glutarique.
This sheet is impregnated with an aqueous composition containing, dry
  • 2 to 15 parts of a binder (starch for example),
  • 0.05 to 4 parts of a base-sensitive agent, manganese chloride,
  • 0.5 to 4 parts of an alkalinity-generating compound, glutaric aldehyde.

On sèche cette feuille .This sheet is dried.

Si on essaie de le falsifier avec une solution aqueuse saturée en sulfite de sodium, il se développe une coloration marron parfaitement visible à l'oeil nu.If we try to falsify it with a saturated aqueous solution of sodium sulfite, it develops a brown color that is perfectly visible to the naked eye.

EXEMPLE 5:EXAMPLE 5:

On réalise une feuille par voie papetière à partir d'une composition fibreuse cellulosique et éventuellement d'autres adjuvants.A sheet is produced by the papermaking route from a cellulosic fibrous composition and possibly other adjuvants.

On imprègne cette feuille avec une composition aqueuse contenant, en sec:

  • 2 à 15 parties d'un liant (amidon par exemple)
  • 0,05 à 2 parties d'un indicateur coloré ,la phénolphtaléine
  • 0,5 à 4 parties d'un composé générateur d'alcalinité, la méthyléthylcétone.
This sheet is impregnated with an aqueous composition containing, dry:
  • 2 to 15 parts of a binder (starch for example)
  • 0.05 to 2 parts of a colored indicator, phenolphthalein
  • 0.5 to 4 parts of an alkalinity-generating compound, methyl ethyl ketone.

On sèche cette feuille.This sheet is dried.

Si on essaie de falsifier le document obtenu à l'aide d'un crayon effaceur, il se développe une coloration rouge.If you try to falsify the document obtained using an eraser, a red color develops.

Si on essaie de le falsifier avec une solution aqueuse saturée en sulfite de sodium, il se développe également une coloration rouge parfaitement visible à l'oeil nu.If we try to falsify it with a saturated aqueous solution of sodium sulfite, it also develops a red coloration perfectly visible to the naked eye.

EXEMPLE 6:EXAMPLE 6

On réalise une feuille par voie papetière à partir d'une composition fibreuse cellulosique et éventuellement d'autres adjuvants.A sheet is produced by the papermaking route from a cellulosic fibrous composition and possibly other adjuvants.

On imprègne cette feuille avec une composition aqueuse contenant ,en sec:

  • 2 à 15 parties d'un liant (amidon par exemple)
  • 0,05 à 2 parties d'un indicateur coloré ,la phénolphtaléine
  • 0,5 à 4 parties d'un composé générateur d'alcalinité comportant indirectement la fonction aldéhyde: l'alcool benzylique mono(poly)hémiformal, commercialisé sous le nom de PREVENTOL D2 par BAYER.
This sheet is impregnated with an aqueous composition containing, dry:
  • 2 to 15 parts of a binder (starch for example)
  • 0.05 to 2 parts of a colored indicator, phenolphthalein
  • 0.5 to 4 parts of an alkalinity-generating compound indirectly comprising the aldehyde function: benzyl alcohol mono (poly) hemiformal, marketed under the name of PREVENTOL D2 by BAYER.

On sèche cette feuille.This sheet is dried.

Si on essaie de falsifier le document obtenu à l'aide d'un crayon effaceur, il se développe une coloration rouge.If you try to falsify the document obtained using an eraser, a red color develops.

Si on essaie de le falsifier avec une solution aqueuse saturée en sulfite de sodium, il se développe également une coloration rouge parfaitement visible à l'oeil nu.If we try to falsify it with a saturated aqueous solution of sodium sulfite, it also develops a red coloration perfectly visible to the naked eye.

Claims (11)

1- Document de sécurité infalsifiable par agent chimique, notamment par le sulfite de sodium, comportant au moins un agent sensible aux bases et comportant en surface et/ou en masse au moins un composé générateur d'alcalinité sous l'action du sulfite de sodium en solution aqueuse. 1- Safety document which cannot be forged by chemical agent, in particular by sodium sulfite, comprising at least one agent sensitive to bases and comprising at the surface and / or in mass at least one compound generating alkalinity under the action of sodium sulfite in aqueous solution. 2- Document selon la revendication 1, caractérisé par le fait que le composé générateur d'alcalinité est un composé comportant directement ou indirectement au moins une fonction aldéhyde ou au moins une fonction cétone. 2- Document according to claim 1, characterized in that the alkalinity generating compound is a compound comprising directly or indirectly at least one aldehyde function or at least one ketone function. 3- Document selon la revendication 2, caractérisé par le fait que le composé aldéhyde est un dialdéhyde. 3- Document according to claim 2, characterized in that the aldehyde compound is a dialdehyde. 4- Document selon la revendication 3, caractérisé par le fait que le dialdéhyde est l'aldéhyde glutarique. 4- Document according to claim 3, characterized in that the dialdehyde is glutaric aldehyde. 5- Document selon la revendications 2, caractérisé par le fait que le composé aldéhyde est l'aldéhyde salycilique. 5- Document according to claims 2, characterized in that the aldehyde compound is salycilic aldehyde. 6- Document selon la revendication 2, caractérisé par le fait que le composé générateur d'alcalinité comportant indirectement une fonction aldéhyde est choisi parmi les hémiformals, les composés soufrés S-méthylol ou les composés azotés N-méthylol. 6- Document according to claim 2, characterized in that the alkalinity generating compound indirectly comprising an aldehyde function is chosen from hemiformals, sulfur compounds S-methylol or nitrogen compounds N-methylol. 7- Document selon la revendication 4, contenant en masse comme agent sensible aux bases, le colorant pour chèque AS vendu par BASF, et comportant en surface de l'aldéhyde glutarique et tel qu'il développe une coloration bleue sous l'action d'une solution aqueuse saturée en sulfite de sodium. 7- Document according to claim 4, containing in mass as agent sensitive to bases, the dye for check AS sold by BASF, and comprising on the surface of glutaraldehyde and such that it develops a blue coloration under the action of a saturated aqueous solution of sodium sulfite. 8- Document selon la revendication 4, comportant en surface comme agent sensible aux bases, de la phénolphtaléine et comportant également en surface de l'aldéhyde glutarique et tel qu'il développe une coloration rouge sous l'action d'une solution aqueuse saturée en sulfite de sodium. 8- Document according to claim 4, comprising on the surface as a base-sensitive agent, phenolphthalein and also comprising on the surface glutaric aldehyde and such that it develops a red coloration under the action of an aqueous solution saturated with sodium sulfite. 9- Document selon la revendication 4, comportant en surface comme agent sensible aux bases fortes du chlorure de manganèse, comportant également en surface de l'aldéhyde glutarique et tel qu'il développe une coloration marron sous l'action d'une solution aqueuse saturée en sulfite de sodium. 9- Document according to claim 4, comprising on the surface as an agent sensitive to strong bases of manganese chloride, also comprising on the surface of glutaraldehyde and such that it develops a brown coloration under the action of a saturated aqueous solution in sodium sulfite. 10- Composition destinée à rendre un document infalsifiable par le sulfite de sodium caractérisée par le fait qu'elle contient : - au moins un composé générateur d'alcalinité, - au moins un agent sensible aux bases fortes et/ou un indicateur coloré, - au moins un liant habituellement utilisé en papeterie. 10- Composition intended to make a document unforgeable by sodium sulfite, characterized in that it contains: - at least one alkalinity-generating compound, - at least one agent sensitive to strong bases and / or a colored indicator, - at least one binder usually used in stationery. 11- Composition selon la revendication 10, caractérisée par le fait qu'elle contient: - au moins un composé générateur d'alcalinité choisi selon l'une des revendications 2 à 8, - au moins un agent sensible aux bases fortes et/ou un indicateur coloré, - au moins un liant habituellement utilisé en papeterie. 11- Composition according to claim 10, characterized in that it contains: - at least one alkalinity-generating compound chosen according to one of claims 2 to 8, - at least one agent sensitive to strong bases and / or a colored indicator, - at least one binder usually used in stationery.
EP19920400058 1991-01-11 1992-01-10 Safety document Expired - Lifetime EP0494828B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9100311 1991-01-11
FR9100311A FR2671566B1 (en) 1991-01-11 1991-01-11 SAFETY DOCUMENT INFALSIFIABLE BY A CHEMICAL AGENT.

Publications (2)

Publication Number Publication Date
EP0494828A1 true EP0494828A1 (en) 1992-07-15
EP0494828B1 EP0494828B1 (en) 1995-04-19

Family

ID=9408627

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19920400058 Expired - Lifetime EP0494828B1 (en) 1991-01-11 1992-01-10 Safety document

Country Status (2)

Country Link
EP (1) EP0494828B1 (en)
FR (1) FR2671566B1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10020873A1 (en) * 2000-04-28 2001-11-08 Mitsubishi Hitec Paper Flensbu Temporary authentification mark for security documents uses a substituted phthalide reacting on contact with an alkaline solution, together with a volatile solvent
WO2010103499A1 (en) * 2009-03-13 2010-09-16 Arjowiggins Security Laser-markable substrate, and associated manufacturing method
WO2012101334A1 (en) 2011-01-25 2012-08-02 Honnorat Recherches & Services Paper that cannot be forged using solvents
WO2013060947A1 (en) 2011-10-26 2013-05-02 Honnorat Recherches & Services Security paper that cannot be falsified using redox agents

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2365656A1 (en) * 1976-05-25 1978-04-21 Arjomari Prioux SECURITY PAPER
FR2399505A1 (en) * 1976-05-25 1979-03-02 Arjomari Prioux Security paper for prepn. of official documents etc. - is coated with or contains oxy:pyrene-tri:sulphonic acid or a salt of the acid

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2365656A1 (en) * 1976-05-25 1978-04-21 Arjomari Prioux SECURITY PAPER
FR2399505A1 (en) * 1976-05-25 1979-03-02 Arjomari Prioux Security paper for prepn. of official documents etc. - is coated with or contains oxy:pyrene-tri:sulphonic acid or a salt of the acid

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10020873A1 (en) * 2000-04-28 2001-11-08 Mitsubishi Hitec Paper Flensbu Temporary authentification mark for security documents uses a substituted phthalide reacting on contact with an alkaline solution, together with a volatile solvent
WO2010103499A1 (en) * 2009-03-13 2010-09-16 Arjowiggins Security Laser-markable substrate, and associated manufacturing method
FR2943074A1 (en) * 2009-03-13 2010-09-17 Arjowiggins Security LASER MARKABLE SUBSTRATE AND METHOD FOR MANUFACTURING THE SAME
WO2012101334A1 (en) 2011-01-25 2012-08-02 Honnorat Recherches & Services Paper that cannot be forged using solvents
US9057159B2 (en) 2011-01-25 2015-06-16 Honnorat Recherches & Services Paper that cannot be forged using solvents
WO2013060947A1 (en) 2011-10-26 2013-05-02 Honnorat Recherches & Services Security paper that cannot be falsified using redox agents

Also Published As

Publication number Publication date
FR2671566A1 (en) 1992-07-17
FR2671566B1 (en) 1993-04-09
EP0494828B1 (en) 1995-04-19

Similar Documents

Publication Publication Date Title
EP1319104B1 (en) Security sheet comprising a transparent or translucent layer
AU634829B2 (en) Lottery ticket paper, a method of manufacturing lottery ticket paper, and the use of said paper in the manufacture of lottery tickets
EP0169750A1 (en) Luminescent security fibres; security documents and other materials containing these fibres
FR2650606A1 (en) INFALSIFIABLE SAFETY PAPER AND USEFUL AQUEOUS OR ORGANIC COMPOSITION, IN PARTICULAR FOR MAKING INFALSIFIABLE PAPER
EP0494828B1 (en) Safety document
EP0174885B1 (en) Security paper and document against forgery by a chemical agent
EP0190087B1 (en) Forge-proof security paper, process for making a paper forge-proof and aqueous or organic composition especially useful in making a paper forge-proof
BE1011817A4 (en) SUPPORT FOR PRINT, WRITE authenticated HEAT AND BY CHEMICAL AGENT unfalsifiable.
JPS5836298A (en) Paper for preventing forgery
EP0440554B1 (en) Combination of a document authenticable and of an authentication composition and process of authentication using such a combination.
GB2084930A (en) Security paper
EP0530059B1 (en) System for the reversibel authentification of a security paper
EP0632162B1 (en) Sheet which is non-forgeable by chemical agents, and non-forgeable document made therefrom
JP2000129596A (en) Paper for preventing falsification
FR2647820A1 (en) INFALSIFIABLE SAFETY PAPER AND USEFUL AQUEOUS OR ORGANIC COMPOSITION, IN PARTICULAR FOR MAKING INFALSIFIABLE PAPER
EP0378029A2 (en) Non-forgeable and non-fluorescent security paper, and document obtained
FR2693749A1 (en) Prepn. of counterfeit-proof paper, or synthetic substrates - by impregnation with a nickel or cobalt salt and an organic acid, carbon di:oxide precursor or reductant with an aldehyde or ketone function (or a mixt.)
FR2694772A1 (en) Counterfeit-proofed foils and security documents obtd. thereby - produced by impregnation with a metallic salt coupled with a co-reactant
RU2243307C1 (en) Securities protected against forgery, method for manufacture and materials used in manufacture (modifications)
EP0428447B1 (en) Security paper comprising a new security thread reacting to falsification
FR2580303A1 (en) Agent and paper for securing against falsification by a chemical agent, and process for its manufacture
DE10021896A1 (en) Recording material (eg of ink-jet, heat-sensitive or self-coloring type) for production of security documents has intermediate layer with embossed markings to serve as a security feature
EP1438194B1 (en) Translucent web-type recording material and a method for producing the same
RU2003129174A (en) SECURITIES PROTECTED FROM FALSE AND METHOD FOR ITS MANUFACTURE
FR2568904A1 (en) Means of security against forgery using a chemical agent, security paper containing such a means, and security document comprising the said security paper

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): FR

17P Request for examination filed

Effective date: 19921029

17Q First examination report despatched

Effective date: 19940901

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): FR

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: ARJO WIGGINS S.A.

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: FR

Ref legal event code: CJ

Ref country code: FR

Ref legal event code: CD

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

Ref country code: FR

Ref legal event code: CD

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20110202

Year of fee payment: 20