EP0632162B1 - Sheet which is non-forgeable by chemical agents, and non-forgeable document made therefrom - Google Patents
Sheet which is non-forgeable by chemical agents, and non-forgeable document made therefrom Download PDFInfo
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- EP0632162B1 EP0632162B1 EP94400090A EP94400090A EP0632162B1 EP 0632162 B1 EP0632162 B1 EP 0632162B1 EP 94400090 A EP94400090 A EP 94400090A EP 94400090 A EP94400090 A EP 94400090A EP 0632162 B1 EP0632162 B1 EP 0632162B1
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- European Patent Office
- Prior art keywords
- acid
- chosen
- acids
- sheet according
- salts
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
- D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
- D21H21/46—Elements suited for chemical verification or impeding chemical tampering, e.g. by use of eradicators
Definitions
- the present invention relates to a falsifiable sheet by chemical agents as well as the safety document obtained and the use of a product as a co-reactant. It relates more particularly to the field of paper safety usable especially for the production of parts of payment or official documents such as checks banking, traveller's checks, accounting ledgers, titles, notarial acts, tickets, and in general all documents for which it is essential to protect against any chemical falsification of writings or seals entered on these said documents.
- the object of the invention is to provide a security sheet containing a salt as a chemical forging agent metallic, the sensitivity of this salt towards agents of falsification being improved, that is to say that the reactions will be more intense than with salt alone or colored reactions will take place when they do not exist, in any case imperceptible with salt alone.
- a further aim is to provide a sheet protected against the greatest number of chemical falsification agents while using as few reagents as possible tampering.
- metal salt a co-reactant chosen in the group formed by certain organic acids or their salts, some derivatives of organic acid, compounds having a function aldehyde reducing agent, the compounds having a reducing function ketone, precursors of carbon dioxide.
- the invention provides a sheet which cannot be forged by agents.
- chemicals comprising at least one means of tampering of which at least one of these means consists of a metal salt associated with a coreagent, characterized by the fact that the coreactive is chosen from the group formed by acids organic as defined in claim 1 or their salts, organic acid derivatives as defined in claim 1, the compounds having a reducing function aldehyde, the compounds having a ketone reducing function, carbon dioxide precursors, being excluded from this groups the compounds comprising a phenolic structure.
- the metal salt is chosen from the salts of cobalt II or III, nickel salts or their mixtures.
- metallic salts they can in particular be chosen among chlorides, sulfates, acetates, nitrates, these salts being anhydrous or hydrated.
- amino acids or sulfonic acids have at least two acid groups. These groupings can be identical, for example the acid cannot contain only carboxylic groups, only sulfonic groups.
- the acid can have both carboxylic groups and sulfonic (s).
- the carboxylic acid is chosen from the group formed by tartaric acid, phthalic acid, acid citric, malonic acid, tricarballylic acid, acid trimelittic.
- the organic acid derivatives are chosen from amides, lactams, anhydrides or even acid chlorides.
- the anhydrides can be of the purely carboxylic or purely sulfonic type or of the mixed type, for example of the sulfocarboxylic type, formed between the carboxylic and sulfonic acid groups.
- the anhydride is of the sulfocarboxylic type, in particular it is 2-sulfo-benzoic anhydride.
- the organic acid can be chosen from amino acids, and more particularly among glutamic acids or asparagines.
- butyraldehyde Preferably used as a compound having a function aldehyde reducing agent, butyraldehyde.
- the carbon dioxide precursor is a carbonate or bicarbonate, such as carbonate or sodium bicarbonate.
- the unforgeable sheet is a paper of purely cellulosic fibrous composition, in part synthetic or possibly purely synthetic.
- Leaf may still be a plastic film, possibly coated.
- the composition of the sheet may contain agents classics used in stationery such as fillers minerals, binders, various resistance agents, bonding products, shading dyes.
- the chemical falsification reagents according to the invention can be added en masse to the composition of the sheet or placed on at least one face of the sheet by impregnation or by coating.
- reagents that are soluble in water or in non-or very weakly toxic solvents or in their mixtures are used, these reagents being applied to the sheet by impregnation using a size press.
- the sheet can also include physical authentication elements such as watermarks, plates, threads or special fibers.
- the sheet is printable by any means of printing and is suitable for writing, in particular with an ink pen or with a ballpoint pen.
- the invention also relates to the security document obtained from of the unforgeable sheet described above as well as the use as defined in claims 11 and 12.
- the wet recovery of the solution is approximately 40 g per 100 g of paper.
- Example 1 To 100 g of the solution of Example 1, 2 g of an organic acid which is malonic acid is added. The sheet is treated as in Example 1.
- the reactivity of the sheets obtained according to these examples is tested comparatively by using a saturated sodium sulfite solution as a falsifying agent.
- a saturated sodium sulfite solution as a falsifying agent.
- an orange coloration is obtained which is more intense than that obtained for example 1.
- Malonic acid therefore participated in the colored reaction between the cobalt salt and the falsifying agent.
- Example 2 A solution is made as in Example 2, but the acid used is a mineral acid, sulfuric acid.
- the colored reaction under the action of a saturated sulfite solution is not more intense than in Example 1.
- Aqueous solutions are produced as in Example 2, the organic acid being a dicarboxylic acid chosen from glutaric acid, citric acid, phthalic acid or tartaric acid, the amount of acid varying between 0 , 5 and 2.5 g per 100 g of the bath of Example 1.
- Example 2 A solution is made as in Example 2, but the cobalt salt is replaced by nickel chloride.
- the co-reactant of the cobalt salt is an amino acid, either L-glutamic acid which has two carboxyl groups, or L-asparagine which has only one carboxyl group.
- L-glutamic acid which has two carboxyl groups
- L-asparagine which has only one carboxyl group.
- Example 2 A solution is produced as in Example 2, but cobalt salt, tricarboxylic acid derived from propane, called tricarballylic acid, is used as co-reactant.
- cobalt salt tricarboxylic acid derived from propane, called tricarballylic acid.
- the potassium permanganate / sodium bisulfite redox couple is applied, there is also an orange coloring, while in the case of Example 1 (case of the cobalt salt alone) there is no clearly visible colored reaction. .
- Example 2 A solution is made as in Example 2, but the acid used is benzoic acid 1,2,4 tricarboxylic called trimelittic acid.
- the acid used is benzoic acid 1,2,4 tricarboxylic called trimelittic acid.
- trimelittic acid we treat a paper as in Example 2. The paper is tested with a saturated sodium sulfite solution, it develops an orange coloring.
- Example 2 To 100 g of the solution of Example 1, 1.45 g of 2-sulfo-benzoic anhydride (mixed anhydride formed between the carboxylic and sulfonic groups) is added. We impregnate a sheet and dry it. The leaf obtained is tested with a saturated sodium sulfite solution, an intense orange reaction develops.
- 2-sulfo-benzoic anhydride mixed anhydride formed between the carboxylic and sulfonic groups
- a plastic sheet is coated with this composition, the quantity deposited dry being 10 g / m 2 .
- the sheet Under the action of a saturated solution of sodium sulfite it develops an orange coloring. Under the action of the potassium permanganate / sodium bisulfite couple, a greenish-brown reaction develops.
- Example 2 To 100 g of the solution of Example 1, 1.7 g of tartaric acid and 1 g of manganese sulphate are added (manganese sulphate is a forging agent known for its reactivity with bleach).
- manganese sulphate is a forging agent known for its reactivity with bleach.
- sulfite Under the action of sulfite, an intense orange color is obtained, bisulfite an orange color, bleach a brown color, sodium hydroxide a brown color, an ink eraser pencil, an orange color , CORECTOR ink a pink to orange halo.
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
- Paper (AREA)
Description
La présente invention concerne une feuille infalsifiable par agents chimiques ainsi que le document de sécurité obtenu et l'utilisation d'un produit comme coréactif. 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 falsifiable sheet by chemical agents as well as the safety document obtained and the use of a product as a co-reactant. It relates more particularly to the field of paper safety usable especially for the production of parts of payment or official documents such as checks banking, traveller's checks, accounting ledgers, titles, notarial acts, tickets, and in general all documents for which it is essential to protect against any chemical falsification of writings or seals entered on these said documents.
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.We already know papers that contain reagents developing a colored reaction under the action of certain agents chemicals used to falsify inscriptions by chemical discoloration of 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, we have describes papers containing reagents sensitive to agents adulteration such as acids, alkalis, agents bleaching chlorines such as chlorine water or bleach, ink erasers; in particular we use pyranine, salt an oxypyrene trisulfonic acid, which develops a coloration fluorescent yellow under the action of an ink erasing pencil.
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, papers have also been described tamper-proof containing specific organic reagents like rutin trihydrate or nostril hydrate.
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-Fe 3+ complex, which is 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 benzéniques 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 compounds has been described. di or trihydroxy benzenes as forging agents, the use of a color reaction activator such as salts or metal oxides, excluding an iron salt II or III, is envisaged.
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 we have described a paper containing as a falsification agent a metal salt preferably of degree of oxidation 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 security sheet containing a salt as a chemical forging agent metallic, the sensitivity of this salt towards agents of falsification being improved, that is to say that the reactions will be more intense than with salt alone or colored reactions will take place when they do not exist, in any case imperceptible with salt alone.
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 chemical falsification agents while using as few reagents as possible tampering.
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 certains acides organiques ou leurs sels, certains 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 objects of the invention are reached if we associate with metal salt, a co-reactant chosen in the group formed by certain organic acids or their salts, some derivatives of organic acid, compounds having a function aldehyde reducing agent, the compounds having a reducing function ketone, precursors of carbon dioxide.
Ainsi l'invention fournit une feuille infalsifiable par agents chimiques comprenant au moins un moyen d'infalsification dont l'un au moins de ces moyens est constitué par un sel métallique associé à un coréactif, caractérisée par le fait que le coréactif est choisi dans le groupe formé par les acides organiques tels que définis dans la revendication 1 ou leurs sels, les dérivés d'acide organique tels que définis dans la revendication 1, les composés ayant une fonction réductrice aldéhyde, les composés ayant une fonction réductrice cétone, les précurseurs de dioxyde de carbone, étant exclus de ce groupe les composés comprenant une structure phénolique.Thus, the invention provides a sheet which cannot be forged by agents. chemicals comprising at least one means of tampering of which at least one of these means consists of a metal salt associated with a coreagent, characterized by the fact that the coreactive is chosen from the group formed by acids organic as defined in claim 1 or their salts, organic acid derivatives as defined in claim 1, the compounds having a reducing function aldehyde, the compounds having a ketone reducing function, carbon dioxide precursors, being excluded from this groups the compounds comprising a phenolic structure.
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 the salts of cobalt II or III, 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 metallic salts, they can in particular be chosen among 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.We note 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 especially under the action of a solution saturated with sodium sulfite or under the action of bisulfite sodium or under the action of redox couples like the potassium permanganate / bisulfite couple of sodium.
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.We also note that in particular the use as co-active 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 the couples redox.
De préférence les acides aminés ou les acides sulfoniques comportent 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. Preferably amino acids or sulfonic acids have at least two acid groups. These groupings can be identical, for example the acid cannot contain only carboxylic groups, only sulfonic groups.
Ces groupements peuvent être aussi différents, par exemple l'acide peut comporter des groupes à la fois carboxylique(s) et sulfonique(s).These groupings can also be different, for example the acid can have both carboxylic groups 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, acid citric, malonic acid, tricarballylic acid, acid trimelittic.
Les dérivés d'acide organique sont choisis parmi les amides,
les lactames, 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-sulfo-benzoique.The organic acid derivatives are chosen from amides, lactams, anhydrides or even acid chlorides. The anhydrides can be of the purely carboxylic or purely sulfonic type or of the mixed type, for example of the sulfocarboxylic type, formed between the carboxylic and sulfonic acid groups.
According to a particular case of the invention, the anhydride is of the sulfocarboxylic type, in particular it is 2-sulfo-benzoic 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 among glutamic acids or asparagines.
On utilise de préférence comme composé ayant une fonction réductrice aldéhyde, le butyraldéhyde.Preferably used as a compound having a function aldehyde reducing agent, 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 one particular case, the carbon dioxide precursor is a carbonate or bicarbonate, such as carbonate or sodium 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 of purely cellulosic fibrous composition, in part synthetic or possibly purely synthetic. Leaf may still be a plastic film, possibly coated. The composition of the sheet may contain agents classics used in stationery such as fillers minerals, binders, various resistance agents, bonding products, shading dyes.
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.
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.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.
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 metallic salts are colored however the quantities used to reveal falsification attempts are weak enough not to color the leaf protect.
On peut ajouter d'autres réactifs d'infalsification déjà connus et compatibles avec ceux selon l'invention.We can add other tampering reagents already known and compatible with those according to the invention.
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 précédemment ainsi que l'utilisation telle que définie dans les revendications 11 et 12.The invention also relates to the security document obtained from of the unforgeable sheet described above as well as the use as defined in claims 11 and 12.
L'invention sera mieux comprise à l'aide des exemples non limitatifs suivants:The invention will be better understood using the examples not following limitations:
On réalise une solution aqueuse de 1185 g contenant :
- 15 g de nitrate de cobalt hexahydraté,
- 150 g d'amidon
- 15 g of cobalt nitrate hexahydrate,
- 150 g starch
On traite une feuille de papier par cette solution à l'aide d'une presse encolleuse. On sèche. We treat a sheet of paper with this solution using of a size press. We dry.
La reprise humide de solution est d'environ 40 g pour 100 g de papier.The wet recovery of the solution is approximately 40 g per 100 g of paper.
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 we treat a leaf with a solution containing only starch and malonic acid, therefore without metal salt, and that we try to falsify it with sodium sulfite, it doesn't no color reaction develops.
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.
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.
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 containing no malonic acid, no coloring develops under the action of the sulfite.
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 imprègne 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.
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.
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.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.
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. .
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.
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.
On teste la feuille obtenue avec une solution de sulfite de
sodium saturée, il se développe une réaction orangée intense.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.
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).
- 1.25% cobalt nitrate hexahydrate,
- 0.1% butyraldehyde,
- 10% sodium acetate (buffer solution).
On traite un papier comme dans l'exemple 2.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.
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
- 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 quantity deposited dry being 10 g / m 2 .
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.
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 color is obtained, bisulfite an orange color, bleach a brown color, sodium hydroxide a brown color, an ink eraser pencil, an orange color , CORECTOR ink a pink to orange halo.
Claims (12)
- Sheet which is non-forgeable by chemical agents, comprising at least one forgeproof means, at least one of these means consisting of a metal salt combined with a co-reagent, characterized in that the co-reagent is a compound chosen from those of the group formed by:organic acids chosen from carboxylic acids containing at least two acid groups, sulphonic acids and amino acids, as well as the salts of these acids,organic acid derivatives chosen from amides, lactams, anhydrides and acid chlorides,compounds with a reductive aldehyde function,compounds with a reductive ketone function,carbon dioxide precursors,compounds comprising a phenolic structure being excluded from this group.
- Sheet according to Claim 1, characterized in that the metal salt is chosen from cobalt II or III salts and nickel salts, or mixtures thereof.
- Sheet according to either of Claims 1 and 2, characterized in that the metal salts are chosen from the nitrates, sulphates and acetates, these salts being anhydrous or hydrated.
- Sheet according to one of Claims 1 to 3, characterized in that the sulphonic acids or amino acids comprise at least two acid groups.
- Sheet according to one of Claims 1 to 3, 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 and trimellitic acid.
- Sheet according to one of Claims 1 to 3, characterized in that the anhydride is 2-sulphobenzoic anhydride.
- Sheet according to one of Claims 1 to 4, characterized in that the amino acids are chosen from glutamic acids and asparagines.
- Sheet according to one of Claims 1 to 3, characterized in that the compound containing a reductive aldehyde function is butyraldehyde.
- 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.
- Non-forgeable document, characterized in that it is obtained from a sheet according to one of the preceding claims.
- Use, as a co-reagent intended to improve the sensitivity of a metal salt used as a forgeproof agent for a sheet, of a product chosen from the family consisting of:organic acids chosen from carboxylic acids containing at least two acid groups, sulphonic acids and amino acids, as well as the salts of these acids,organic acid derivatives chosen from amides, lactams, anhydrides and acid chlorides,compounds with a reductive aldehyde function,compounds with a reductive ketone function,carbon dioxide precursors,compounds comprising a phenolic structure being excluded from this group.
- Use according to Claim 11, characterized in that the metal salt is a cobalt II or III salt or a nickel salt or a mixture of these salts.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9307885A FR2694772B1 (en) | 1992-07-15 | 1993-06-29 | INFALSIFIABLE SHEET BY CHEMICAL AGENT AND SAFETY DOCUMENT OBTAINED. |
| FR9307885 | 1993-06-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0632162A1 EP0632162A1 (en) | 1995-01-04 |
| EP0632162B1 true EP0632162B1 (en) | 1999-12-08 |
Family
ID=9448659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94400090A Expired - Lifetime EP0632162B1 (en) | 1993-06-29 | 1994-01-14 | Sheet which is non-forgeable by chemical agents, and non-forgeable document made therefrom |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0632162B1 (en) |
| DE (1) | DE69421965T2 (en) |
| ES (1) | ES2142386T3 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU6697198A (en) * | 1997-03-14 | 1998-10-12 | Georgia-Pacific Corporation | Security paper |
| FR2970716B1 (en) | 2011-01-25 | 2013-09-06 | Honnorat Rech S & Services | SAFETY PAPER INFALSIFIABLE TO SOLVENTS |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0378029A2 (en) * | 1988-12-07 | 1990-07-18 | Aussedat-Rey | Non-forgeable and non-fluorescent security paper, and document obtained |
Family Cites Families (2)
| 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.) |
-
1994
- 1994-01-14 ES ES94400090T patent/ES2142386T3/en not_active Expired - Lifetime
- 1994-01-14 DE DE1994621965 patent/DE69421965T2/en not_active Expired - Lifetime
- 1994-01-14 EP EP94400090A patent/EP0632162B1/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0378029A2 (en) * | 1988-12-07 | 1990-07-18 | Aussedat-Rey | Non-forgeable and non-fluorescent security paper, and document obtained |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2142386T3 (en) | 2000-04-16 |
| EP0632162A1 (en) | 1995-01-04 |
| DE69421965D1 (en) | 2000-01-13 |
| DE69421965T2 (en) | 2000-06-29 |
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