EP0632162A1 - Sheet which is non-forgeable by chemical means, and security document made therefrom - Google Patents

Sheet which is non-forgeable by chemical means, and security document made therefrom 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
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EP
European Patent Office
Prior art keywords
acid
sheet according
chosen
acids
sheet
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Granted
Application number
EP94400090A
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German (de)
French (fr)
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EP0632162B1 (en
Inventor
Alain Barthez
Sandrine Dubois
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ArjoWiggins SAS
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ArjoWiggins SAS
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Priority claimed from FR9307885A external-priority patent/FR2694772B1/en
Application filed by ArjoWiggins SAS filed Critical ArjoWiggins SAS
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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

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

Abstract

The sheet contains at least as forgery-proofing agent a metal salt in combination with a coreactant chosen from the group consisting of organic acids or their salts, organic acid derivatives, compounds which have an aldehyde reducing functional group, compounds containing a ketone reducing functional group and carbon dioxide precursors. Application to paper for cheques.

Description

La présente invention concerne une feuille infalsifiable par agents chimiques ainsi que le document de sécurité obtenu. Elle concerne plus particulièrement le domaine des papiers de sécurité utilisables notamment pour la réalisation de pièces de paiement ou de documents officiels tels que les chèques bancaires, chèques de voyages, livres d'écritures comptables, titres, actes notariés, titres de transport, et de façon générale tous documents pour lesquels il est indispensable de se prémunir contre toute falsification chimique des écritures ou cachets portés sur ces dits documents.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.

On connait déjà des papiers qui comportent des réactifs développant une réaction colorée sous l'action de certains agents chimiques utilisés pour falsifier des inscriptions par décoloration chimique des encres.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.

Dans les brevets FR-A-2365656, FR-A-2399505, FR-E-2402739, on a décrit des papiers contenant des réactifs sensibles aux agents d'infalsification comme les acides, les alcalis, les agents chlorés décolorants comme l'eau de chlore ou l'eau de javel, les crayons effaceurs d'encre; on utilise notamment la pyranine, sel d'un acide oxypyrène trisulfonique, qui développe une coloration jaune fluorescente sous l'action d'un crayon effaceur d'encre.In the patents FR-A-2365656, FR-A-2399505, FR-E-2402739, papers have been described containing reagents sensitive to falsification agents such as acids, alkalis, chlorinated bleaching agents such as water chlorine or bleach, ink erasers; in particular, pyranine, salt of an oxypyrene trisulfonic acid, which develops a fluorescent yellow coloration under the action of an ink erasing pencil, is used.

Dans la demande FR-A-2647820 on a décrit également des papiers infalsifiables contenant des réactifs organiques particuliers comme la rutine trihydratée ou la narigine hydratée.In application FR-A-2647820, tamper-proof papers containing particular organic reagents such as rutin trihydrate or narigin hydrate have also been described.

Dans le brevet EP-B-174885 on a décrit également un papier contenant le complexe 2-2' bipyridyle-Fe³⁺, sensible aux couples de falsification oxydo-réducteurs et aux réducteurs comme le bisulfite.In patent EP-B-174885, a paper has also been described containing the 2-2 'bipyridyl-Fe³⁺ complex, sensitive to pairs of redox falsifications and to reducers such as bisulfite.

Dans la demande FR-A-2650606 on a décrit l'emploi de composés benzèniques di ou trihydroxylés comme agents d'infalsification, l'emploi d'un activateur de la réaction colorée comme les sels ou les oxydes métalliques, à l'exclusion d'un sel de fer II ou III, est envisagé.In application FR-A-2650606, the use of di or trihydroxy benzene compounds has been described as forging agents, the use of an activator of the colored reaction such as the salts or metal oxides, excluding an iron salt II or III, is contemplated.

Dans les demandes FR-A-2643661, FR-A-2620146 et FR-A-2654446 déposées par la Demanderesse on a décrit un papier contenant comme agent d'infalsication un sel de métal de préférence de degré d'oxydation II et en particulier un sel de cobalt II qui donne une réaction orangée sous l'action du bisulfite de sodium.In applications FR-A-2643661, FR-A-2620146 and FR-A-2654446 filed by the Applicant, a paper has been described containing as a falsification agent a metal salt preferably of oxidation state II and in particular a cobalt II salt which gives an orange reaction under the action of sodium bisulfite.

Dans la demande EP-A-378029 on a également décrit un papier contenant comme réactif d'infalsification, un sel de cobalt II ou III mais ce sel est associé à un coréactant de caractère réducteur et de structure phénolique.
Par rapport à l'emploi d'un sel de cobalt seul, le coréactant réducteur de type phénolique permet d'obtenir une réaction colorée plus intense avec les couples d'infalsification oxydo-réducteurs dans les conditions de tests préconisées dans le domaine des papiers infalsifiables cependant la coloration n'est pas améliorée pour les autres agents d'infalsification notamment pour les solutions de sulfite de sodium.In application EP-A-378029 a paper has also been described containing as a falsification reagent, a cobalt II or III salt, but this salt is associated with a co-reactant of reducing nature and of phenolic structure.
Compared to the use of a cobalt salt alone, the reducing co-reactant of the phenolic type makes it possible to obtain a more intense colored reaction with the oxidation-reduction infalsification pairs under the test conditions recommended in the field of tamper-proof papers. however, the coloring is not improved for the other forging agents, in particular for the sodium sulfite solutions.

Le but de l'invention est de fournir une feuille de sécurité contenant comme agent d'infalsification chimique un sel métallique, la sensibilité de ce sel vis-à-vis des agents de falsification étant améliorée c'est-à-dire que les réactions colorées seront plus intenses qu'avec le sel seul ou que des réactions colorées auront lieu alors qu'elles sont inexistantes, en tout cas imperceptibles avec le sel seul.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.

Un but complémentaire est de fournir une feuille protégée contre le plus grand nombre d'agents chimiques de falsification tout en utilisant le plus petit nombre possible de réactifs d'infalsification.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.

La Demanderesse a découvert que les buts de l'invention sont atteints si on associe au sel métallique, un coréactif choisi dans le groupe formé par les acides organiques ou leurs sels, les dérivés d'acide organique, les composés ayant une fonction réductrice aldéhyde, les composés ayant une fonction réductrice cétone, les précurseurs de dioxyde de carbone.The Applicant has discovered that the aims of the invention are achieved if 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.

Ainsi l'invention fournit une feuille infalsifiable par agents chimiques caractérisée par le fait qu'elle contient au moins comme agent d'infalsication un sel métallique associé à un coréactif choisi dans le groupe formé par les acides organiques ou leurs sels, les dérivés d'acide organique, les composés ayant une fonction réductrice aldéhyde, les composés ayant une fonction réductrice cétone, les précurseurs de dioxyde de carbone.Thus, 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.

De préférence le sel métallique est choisi parmi les sels de cobalt II ou III, les sels de nickel ou leurs mélanges.Preferably the metal salt is chosen from cobalt II or III salts, nickel salts or their mixtures.

Comme sels métalliques on peut en particulier les choisir parmi les chlorures, les sulfates, les acétates, les nitrates, ces sels étant anhydres ou hydratés.As metal salts, it is possible in particular to choose them from chlorides, sulfates, acetates, nitrates, these salts being anhydrous or hydrated.

On note qu'en particulier l'utilisation d'un acide organique, son sel ou d'un dérivé permet d'obtenir une réaction colorée d'une grande intensité notamment sous l'action d'une solution saturée de sulfite de sodium ou sous l'action du bisulfite de sodium ou encore sous l'action des couples oxydo-réducteurs comme le couple permanganate de potassium / bisulfite de sodium.It is noted that in particular the use of 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.

On note aussi qu'en particulier l'utilisation comme coréactif d'un réducteur ayant une fonction aldéhyde ou cétone ou d'un précurseur de dioxyde de carbone donne notamment la sensibilité de la réaction du sel métallique aux couples oxydo-réducteurs.It is also noted that in particular the use as co-reactant of a reducing agent having an aldehyde or ketone function or of a carbon dioxide precursor gives in particular the sensitivity of the reaction of the metal salt to redox couples.

De préférence les acides organiques sont choisis parmi les acides carboxyliques ou les acides sulfoniques.
De préférence l'acide organique comporte au moins deux groupements acides. Ces groupements peuvent être identiques, par exemple l'acide ne peut comporter que des groupes carboxyliques, que des groupes sulfoniques . Ces groupements peuvent être aussi différents, par exemple l'acide peut comporter des groupes à la fois carboxylique(s) et sulfonique(s).Preferably, the organic acids are chosen from carboxylic acids or sulfonic acids.
Preferably 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).

En particulier l'acide carboxylique est choisi dans le groupe formé par l'acide tartrique, l'acide phtalique, l'acide citrique, l'acide malonique, l'acide tricarballylique, l'acide trimélittique.In particular, the carboxylic acid is chosen from the group formed by tartaric acid, phthalic acid, citric acid, malonic acid, tricarballylic acid, trimelittic acid.

Les dérivés d'acide organique peuvent être choisis parmi les amides, les lactames, les esters, les anhydrides ou encore les chlorures d'acide.
Les anhydrides peuvent être de type purement carboxylique ou purement sulfonique ou de type mixte comme par exemple de type sulfocarboxylique, formé entre les groupes acides carboxylique et sulfonique.
Selon un cas particulier de l'invention, l'anhydride est de type sulfocarboxylique, en particulier c'est l'anhydride 2-sulfobenzoique.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.
According to a particular case of the invention, the anhydride is of the sulfocarboxylic type, in particular it is 2-sulfobenzoic anhydride.

Dans un cas particulier de l'invention, l'acide organique peut être choisi parmi les acides aminés, et plus particulièrement parmi les acides glutamiques ou les asparagines.In a particular case of the invention, the organic acid can be chosen from amino acids, and more particularly from glutamic acids or asparagines.

On utilise de préférence comme composé ayant une fonction réductrice aldéhyde, le butyraldéhyde.Preferably used as compound having an aldehyde reducing function, butyraldehyde.

Dans un cas particulier, le précurseur de dioxyde de carbone est un carbonate ou un bicarbonate, comme par exemple le carbonate ou le bicarbonate de sodium.In a particular case, the carbon dioxide precursor is a carbonate or a bicarbonate, such as, for example, sodium carbonate or bicarbonate.

Selon l'invention, la feuille infalsifiable est un papier de composition fibreuse purement cellulosique, en partie synthétique ou éventuellement purement synthétique. La feuille peut être encore un film plastique, éventuellement couché.
La composition de la feuille peut contenir des agents classiques utilisés en papeterie comme par exemple les charges minérales, des liants, des agents de résistance divers, des produits de collage, des colorants de nuançage.According to the invention, 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.

Les réactifs chimiques d'infalsification selon l'invention peuvent être ajoutés en masse à la composition de la feuille ou disposés sur au moins une face de la feuille par imprégnation ou par couchage.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.

De préférence on utilise des réactifs solubles dans l'eau ou dans des solvants non ou très faiblement toxiques ou dans leurs mélanges, ces réactifs étant apportés sur la feuille par imprégnation à l'aide d'une presse encolleuse.Preferably, 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.

Certains sels métalliques sont colorés cependant les quantités utilisées pour révéler les tentatives de falsification sont suffisamment faibles pour ne pas colorer la feuille à protéger.Some metal salts are colored, however the quantities used to reveal attempts at falsification are small enough not to color the sheet to be protected.

On peut ajouter d'autres réactifs d'infalsification déjà connus et compatibles avec ceux selon l'invention.Other adulteration reagents already known and compatible with those according to the invention can be added.

La feuille peut comporter aussi des éléments d'authentification physiques comme les filigranes, planchettes, fils ou fibres spéciaux.
La feuille est imprimable par tout moyen d'impression et est apte à l'écriture, notamment avec un stylo à encre ou avec un stylo à bille.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.

L'invention vise aussi le document de sécurité obtenu à partir de la feuille infalsifiable décrite précedemment.The invention also relates to the security document obtained from the tamper-evident sheet described above.

L'invention sera mieux comprise à l'aide des exemples non limitatifs suivants:The invention will be better understood using the following nonlimiting examples:

EXEMPLE COMPARATIF 1 :COMPARATIVE EXAMPLE 1:

On réalise une solution aqueuse de 1185 g contenant :

  • 15 g de nitrate de cobalt hexahydraté,
  • 150 g d'amidon

On traite une feuille de papier par cette solution à l'aide d'une presse encolleuse. On sèche.An aqueous solution of 1185 g is produced containing:
  • 15 g of cobalt nitrate hexahydrate,
  • 150 g starch

A sheet of paper is treated with this solution using a size press. We dry.

La reprise humide de solution est d'environ 40 g pour 100 g de papier.The wet take-up of the solution is approximately 40 g per 100 g of paper.

EXEMPLE 2 :EXAMPLE 2:

A 100g de la solution de l'exemple 1, on ajoute 2g d'un acide organique qui est l'acide malonique.
On traite la feuille comme dans l'exemple 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.

On teste comparativement la réactivité des feuilles obtenues selon ces exemples en utilisant comme agent de falsification une solution saturée de sulfite de sodium. Pour l'exemple 2 selon l'invention on obtient une coloration orange plus intense que celle obtenue pour l'exemple 1.
L'acide malonique a donc participé à la réaction colorée entre le sel de cobalt et l'agent de falsification.The reactivity of the sheets obtained according to these examples is tested comparatively by using a saturated sodium sulfite solution as a falsifying agent. For example 2 according to the invention, 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.

Si on traite une feuille par une solution ne contenant que de l'amidon et de l'acide malonique, donc sans sel métallique, et qu'on essaie de la falsifier avec le sulfite de sodium, il ne se développe pas de réaction colorée.If a leaf is treated with a solution containing only starch and malonic acid, therefore without metallic salt, and an attempt is made to falsify it with sodium sulphite, a color reaction does not develop.

EXEMPLE COMPARATIF 3 :COMPARATIVE EXAMPLE 3:

On réalise une solution comme dans l'exemple 2 mais l'acide utilisé est un acide minéral, l'acide sulfurique.
La réaction colorée sous l'action d'une solution de sulfite saturée n'est pas plus intense que dans l'exemple 1.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.

EXEMPLE 4 :EXAMPLE 4:

On réalise des solutions aqueuses comme dans l'exemple 2, l'acide organique étant un acide dicarboxylique choisi parmi l'acide glutarique, l'acide citrique, l'acide phtalique ou l'acide tartrique, la quantité d'acide variant entre 0,5 et 2,5g pour 100g du bain de l'exemple 1.
On imprègne des papiers avec ces différentes solutions. On sèche.
On teste les feuilles traitées avec une solution saturée de sulfite de sodium. Dans chaque cas, une coloration orange se développe, l'intensité de la couleur étant nettement supérieure à celle obtenue pour l'exemple 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.
We impregnate papers with these different solutions. We dry.
The treated leaves are tested with a saturated solution of sodium sulfite. In each case, an orange coloration develops, the intensity of the color being much higher than that obtained for example 1.

EXEMPLE 5 :EXAMPLE 5:

On réalise une solution comme dans l'exemple 2 mais on remplace le sel de cobalt par le chlorure de nickel.
On traite un papier comme dans l'exemple 2.
Sous l'action d'une solution de sulfite saturée il se développe une coloration rose intense.
Si on imprègne le papier avec une solution ne contenant pas d'acide malonique, il ne se développe aucune coloration sous l'action du sulfite.A solution is made as in Example 2, but the cobalt salt is replaced by nickel chloride.
We treat a paper as in Example 2.
Under the action of a saturated sulfite solution, an intense pink color develops.
If the paper is impregnated with a solution which does not contain malonic acid, no coloring develops under the action of sulfite.

EXEMPLE 6 :EXAMPLE 6

On réalise des solutions comme dans l'exemple 2 mais le coréactif du sel de cobalt est un acide aminé soit l'acide L-glutamique qui a deux groupes carboxyles, soit la L-asparagine qui a un seul groupe carboxyle.
On imprégne des feuilles de papier avec ces différentes solutions; on sèche.
Sous l'action d'une solution saturée de sulfite de sodium il se développe une coloration jaune intense, quelque soit l'acide aminé.Solutions are produced as in Example 2, but 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.
We impregnate sheets of paper with these different solutions; we dry.
Under the action of a saturated solution of sodium sulfite it develops an intense yellow coloring, whatever the amino acid.

EXEMPLE 7 :EXAMPLE 7:

On réalise une solution comme dans l'exemple 2 mais on utilise comme coréactif du sel de cobalt, l'acide tricarboxylique dérivé du propane appelé acide tricarballylique.
On traite un papier comme dans l'exemple 2.
On applique une solution saturée de sulfite de sodium; il se développe une coloration orangée plus intense que dans l'exemple 1.A solution is produced as in Example 2, but cobalt salt, tricarboxylic acid derived from propane, called tricarballylic acid, is used as co-reactant.
We treat a paper as in Example 2.
Apply a saturated solution of sodium sulfite; a more intense orange color develops than in Example 1.

On applique le couple oxydo-réducteur permanganate de potassium / bisulfite de sodium, il se développe également une coloration orangée alors que dans le cas de l'exemple 1 (cas du sel de cobalt seul) il n'y pas de réaction colorée bien visible.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. .

EXEMPLE 8 :EXAMPLE 8:

On réalise une solution comme dans l'exemple 2 mais on utilise comme acide, l'acide benzoique 1,2,4 tricarboxylique appelé acide trimélittique.
On traite un papier comme dans l'exemple 2.
On teste le papier avec une solution de sulfite de sodium saturée, il se développe une coloration orangée.A solution is made as in Example 2, but the acid used is benzoic acid 1,2,4 tricarboxylic called 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.

EXEMPLE 9 :EXAMPLE 9:

A 100g de la solution de l'exemple 1, on ajoute 1,45g d'anhydride 2-sulfo-benzoique (anhydride mixte formé entre les groupes carboxylique et sulfonique).
On en imprègne une feuille et on la sèche.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.

On teste la feuille obtenue avec une solution de sulfite de sodium saturée, il se développe une réaction orangée intense.The leaf obtained is tested with a saturated sodium sulfite solution, an intense orange reaction develops.

EXEMPLE 10 :EXAMPLE 10:

On réalise une solution aqueuse contenant par rapport au bain total, en poids :

  • 1,25% de nitrate de cobalt hexahydraté,
  • 0,1% de butyraldéhyde,
  • 10% d'acétate de sodium (solution tampon).

On traite un papier comme dans l'exemple 2.An aqueous solution is produced containing, relative to the total bath, by weight:
  • 1.25% cobalt nitrate hexahydrate,
  • 0.1% butyraldehyde,
  • 10% sodium acetate (buffer solution).

We treat a paper as in Example 2.

Sous l'action d'une solution saturée de sulfite de sodium il se développe une coloration jaune.
Sous l'action du couple permanganate de potassium / bisulfite de sodium, il se développe une réaction orangée.
Sous l'action de l'eau de javel, il se développe une réaction verte.Under the action of a saturated solution of sodium sulfite a yellow coloration develops.
Under the action of the potassium permanganate / sodium bisulfite couple, an orange reaction develops.
Under the action of bleach, a green reaction develops.

EXEMPLE 11 :EXAMPLE 11:

On réalise une composition aqueuse de 1 kg contenant :

  • 11,4g de nitrate de cobalt hexahydraté,
  • 100 g de carbonate de sodium,
  • 15g d'un liant latex
An aqueous composition of 1 kg is produced containing:
  • 11.4 g of cobalt nitrate hexahydrate,
  • 100 g of sodium carbonate,
  • 15g of a latex binder

On couche une feuille plastique avec cette composition, la quantité déposée en sec étant de 10 g/m² .
On teste la feuille.
Sous l'action d'une solution saturée de sulfite de sodium il se développe une coloration orangée.
Sous l'action du couple permanganate de potassium / bisulfite de sodium il se développe une réaction brun-verdâtre.A plastic sheet is coated with this composition, the amount deposited dry being 10 g / m².
We test 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.

EXEMPLE 13 : EXAMPLE 13 :

A 100g de la solution de l'exemple 1, on ajoute 1,7g d'acide tartrique et lg de sulfate de manganèse (le sulfate de manganèse est un agent d'infalsification connu pour sa réactivité à l'eau de javel).
On traite un papier comme dans l'exemple 2.
Sous l'action du sulfite on obtient une coloration orangée intense, du bisulfite une coloration orange, de l'eau de javel une coloration marron, de l'hydroxyde de sodium une coloration marron, d'un crayon effaceur d'encre une coloration orangée, du CORECTOR encre une auréole rose à orangée.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.

Claims (13)

Feuille infalsifiable par agents chimiques caractérisée par le fait qu'elle contient au moins comme agent d'infalsification un sel métallique associé à un coréactif choisi dans le groupe formé par les acides organiques ou leurs sels, les dérivés d'acide organique, les composés ayant une fonction réductrice aldéhyde, les composés ayant une fonction réductrice cétone, les précurseurs de dioxyde de carbone.Sheet which cannot be forged by chemical agents, characterized in that it contains at least as a forging agent a metal salt associated with a coreagent chosen from the group formed by organic acids or their salts, organic acid derivatives, compounds having an aldehyde reducing function, the compounds having a ketone reducing function, carbon dioxide precursors. Feuille selon la revendication 1, caractérisée par le fait que le sel métallique est choisi parmi les sels de cobalt II ou III, les sels de nickel ou leurs mélanges.Sheet according to claim 1, characterized in that the metal salt is chosen from cobalt II or III salts, nickel salts or their mixtures. Feuille selon l'une des revendications 1 à 2, caractérisée par le fait que les sels métalliques sont choisis parmi les nitrates, les chlorures, les sulfates, les acétates, ces sels étant anhydres ou hydratés.Sheet according to one of claims 1 to 2, characterized in that the metal salts are chosen from nitrates, chlorides, sulfates, acetates, these salts being anhydrous or hydrated. Feuille selon l'une des revendications 1 à 3, caractérisée par le fait que les acides organiques sont choisis parmi les acides carboxyliques ou les acides sulfoniques.Sheet according to one of claims 1 to 3, characterized in that the organic acids are chosen from carboxylic acids or sulfonic acids. Feuille selon l'une des revendications 1 à 4, caractérisée par le fait que les acides organiques comportent au moins deux groupements acides.Sheet according to one of claims 1 to 4, characterized in that the organic acids comprise at least two acid groups. Feuille selon la revendication 5, caractérisée par le fait que les acides carboxyliques sont choisis dans le groupe formé par l'acide malonique, l'acide glutarique, l'acide phtalique, l'acide citrique, l'acide tartrique, l'acide tricarballylique, l'acide trimélittique.Sheet according to claim 5, characterized in that the carboxylic acids are chosen from the group formed by malonic acid, glutaric acid, phthalic acid, citric acid, tartaric acid, tricarballylic acid , trimelittic acid. Feuille selon l'une des revendications 1 à 3, caractérisée par le fait que les dérivés d'acide organique sont choisis parmi les amides, les lactames, les esters, les anhydrides, les chlorures d'acide.Sheet according to one of claims 1 to 3, characterized in that the organic acid derivatives are chosen from amides, lactams, esters, anhydrides, acid chlorides. Feuille selon la revendication 7, caractérisée par le fait que l'anhydride est l'anhydride 2-sulfo-benzoique.Sheet according to claim 7, characterized in that the anhydride is 2-sulfo-benzoic anhydride. Feuille selon l'une des revendications 1 à 5, caractérisée par le fait que les acides organiques sont des acides aminés.Sheet according to one of claims 1 to 5, characterized in that the organic acids are amino acids. Feuille selon la revendication 9, caractérisée par le fait que les acides aminés sont choisis parmi les acides glutamiques ou les asparagines.Sheet according to claim 9, characterized in that the amino acids are chosen from glutamic acids or asparagines. Feuille selon l'une des revendications 1 à 3, caractérisée par le fait que le composé ayant une fonction réductrice aldéhyde est le butyraldéhyde.Sheet according to one of claims 1 to 3, characterized in that the compound having an aldehyde reducing function is butyraldehyde. Feuille selon l'une des revendications 1 à 3, caractérisée par le fait que les précurseurs de dioxyde de carbone sont des carbonates ou des bicarbonates, notamment le carbonate ou le bicarbonate de sodium.Sheet according to one of claims 1 to 3, characterized in that the carbon dioxide precursors are carbonates or bicarbonates, in particular sodium carbonate or bicarbonate. Document infalsifiable caractérisé par le fait qu'il est obtenu à partir d'une feuille selon l'une des revendications précédentes.An unforgeable document characterized in that it is obtained from a sheet according to one of the preceding claims.
EP94400090A 1993-06-29 1994-01-14 Sheet which is non-forgeable by chemical agents, and non-forgeable document made therefrom Expired - Lifetime EP0632162B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9307885 1993-06-29
FR9307885A FR2694772B1 (en) 1992-07-15 1993-06-29 INFALSIFIABLE SHEET BY CHEMICAL AGENT AND SAFETY DOCUMENT OBTAINED.

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EP0632162A1 true EP0632162A1 (en) 1995-01-04
EP0632162B1 EP0632162B1 (en) 1999-12-08

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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 (en) 2011-01-25 2012-08-02 Honnorat Recherches & Services Paper that cannot be forged using solvents

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE635442C (en) * 1934-03-21 1936-09-17 Papierfabrik Spechthausen Akt Process for the production of security paper
FR2693749A1 (en) * 1992-07-15 1994-01-21 Arjo Wiggins Sa 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.)

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2639970B1 (en) * 1988-12-07 1991-09-20 Aussedat Rey NON-FLUORESCENT, NON-FLUORESCENT SECURITY PAPER AND DOCUMENT OBTAINED

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE635442C (en) * 1934-03-21 1936-09-17 Papierfabrik Spechthausen Akt Process for the production of security paper
FR2693749A1 (en) * 1992-07-15 1994-01-21 Arjo Wiggins Sa 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.)

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 (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

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ES2142386T3 (en) 2000-04-16
DE69421965T2 (en) 2000-06-29
EP0632162B1 (en) 1999-12-08
DE69421965D1 (en) 2000-01-13

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