WO2013060947A1 - Security paper that cannot be falsified using redox agents - Google Patents
Security paper that cannot be falsified using redox agents Download PDFInfo
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- WO2013060947A1 WO2013060947A1 PCT/FR2012/000434 FR2012000434W WO2013060947A1 WO 2013060947 A1 WO2013060947 A1 WO 2013060947A1 FR 2012000434 W FR2012000434 W FR 2012000434W WO 2013060947 A1 WO2013060947 A1 WO 2013060947A1
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- dry weight
- paper
- security paper
- tamperproof
- barium carbonate
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Classifications
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- 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
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/12—Organo-metallic compounds
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/18—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only forming new compounds in situ, e.g. within the pulp or paper, by chemical reaction with itself, or other added substances, e.g. by grafting on the fibres
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
-
- 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
-
- 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/385—Oxides, hydroxides or carbonates
Definitions
- the invention relates to a tamper-resistant security paper vis-à-vis oxidation-reducing agents.
- Documents such as checks, vouchers, passports, certain gift vouchers, identity documents and other documents such as medical prescriptions, title deeds and other vital documents contain personalized information that may be modified by counterfeiters.
- the changes involve using clearing agents to remove variable data from documents and to post new information, a new recipient, or another amount on a check, for example.
- the erasing agents used by counterfeiters are all those likely to be found commercially, it is particularly used bleach, acids, bases, redox combinations, solvents and very generally all the products capable of erasing inks such as for example hairsprays, white spirit, brake fluid, liquid stain removers, etc.
- the known tamper-proof products it may especially be mentioned those described in the patent FR 2,650,606 which allow a paper treatment vis-à-vis bases, erasers and alkaline reducing agents or EP 190 087 which more specifically indicates reagents for erasers.
- EP 494 828 indicates an infalsifiability reaction with respect to sodium sulfite. Acid reactants have been known for many, many years, for example, US 322,130 dated July 14, 1885 or US 643,084 of the year 1900.
- Tamper reactions with respect to the redox combinations are known from documents US Pat. No. 4,478,681, EP 174,885 and EP 378,029, all of these solutions, however, have important defects, in particular as regards the toxicity of the compounds. the chemicals used or the instability of the reagents with respect to air oxidation, resulting in paper aging, which results in a significant loss of whiteness and reactivity.
- the tamperproof paper according to the invention aims to respond to this problem for tamper-resistant reactions with respect to redox combinations based on the use of permanganate as an oxidizing agent.
- tamperproof security paper vis-à-vis tampering attempts with redox-based combinations based on permanganate is characterized in that it comprises on its surface and / or in its mass barium carbonate, and in that that it is manufactured with components introducing less than 3% by dry weight relative to the dry weight of paper of the salts comprising sulphate or sulphite ions.
- the advantages of the tamperproof security paper according to the invention are multiple: the paper obtained is very white and its whiteness is not altered in time since the barium carbonate is insensitive to the oxidation of the air, moreover the product is non-fluorescent which is an added benefit,
- barium carbonate Due to its slightly alkaline nature barium carbonate allows the realization of security papers in neutral bonding, which is recognized for its stability over time,
- barium carbonate Because of its specific physical characteristics barium carbonate also brings opacity to paper without the need to add a charge such as titanium oxide for this, this actually results in a saving of material and a lower cost price of paper,
- the invention relates to a paper treated in its mass or on its surface with barium carbonate to be unfalsifiable vis-à-vis erasing agents comprising oxido-reducing combinations based on potassium permanganate as an oxidizing agent.
- Such combinations in order to erase variable data on documents, written or printed, concern for example:
- the invention also aims to treat the paper so that the redox-based combinations of permanganate applied by the forgers lead to a coloring of the paper which is definitive, irreversible, the paper once colored by a combination such that previously described can not be discolored by the application of another chemical agent, in this the tamper-proof reaction is quite interesting and original.
- the paper has the least possible sulphate or sulphite ions or compounds capable of converting barium carbonate to barium sulfate, which is inactive with respect to said erasing agents.
- Such ions are traditionally brought into the paper by the sulphate of alumina which is essential for the development of the paper gluing in an acid medium, the paper must therefore be glued in a so-called “neutral” or “pseudoneutre” medium in the jargon paper, c ie, pasted without the rosin-alumina sulphate mixture.
- Another source of sulphate ions in the security papers comes from the addition of manganese sulphate, copper sulphate, cobalt sulphate or compounds bringing salts containing such ions in the paper, these products are especially used. to bring a color reaction against erasing attempts with bleach, alkalis and acids.
- manganese chloride or other components which develop the same known reactions without the addition of sulfate ions, according to another variant of the organic components can also be used. substitute for these mineral reagents.
- the paper in which the infeasible reagent is introduced with respect to the redox combinations is therefore quite particular in its composition which must contain as little sulphate or sulphite ions in its composition and that all along its preparation. Ideally the paper should be free of such ions but in practice this is not possible and a minimal amount is still tolerable.
- the infeasible security paper with respect to the attempts of falsification with redox-based combinations based on permanganate is characterized in that it comprises on its surface and / or in its mass barium carbonate. and in that it is manufactured with components introducing less than 3% by dry weight, based on the dry weight of paper, of salts comprising sulphate or sulphite ions.
- the infeasible security paper comprises at least 1% and at most 20% of barium carbonate by dry weight relative to the dry weight of said security paper.
- the infeasible security paper comprises between 2% and 10% of barium carbonate by dry weight relative to the dry weight of said security paper and is manufactured with components introducing less than 1% by dry weight relative to the weight.
- dry paper salts containing sulphate or sulphite ions are preferably used.
- the amount of barium carbonate to be introduced into the paper depends on the level of coloration desired for the infeasible reaction and the amount of sulfite or sulphate ions present in the papermaking process. If such poisons are present in a significant amount, either by input into the pulp, or by introduction to the size-press, or by introduction by a subsequent surface treatment of the paper, for example by coating or by varnishing, the The amount to be introduced of barium carbonate will have to be adapted and higher than if these ions are absent.
- the barium carbonate is advantageously introduced into the paper at the time of preparation of the dough, for example in the pulper or in the traditional method of introducing the mass load.
- the barium carbonate can be introduced in the form of a powder, a "slurry" which is a powder dispersed in water, or manufactured in-situ by a mixture of sodium carbonate in the presence of a soluble salt of barium .
- a preparation produced in situ in the paper pulp has the advantage of coating the paper fibers with barium carbonate with increased reactivity compared to tamper-resistant reactions.
- the barium carbonate can also be introduced once the paste has been drained, by the size-press or by any coating device placed in or out of the paper machine, in particular by a coating device, so as to bring the reagent to the surface of the paper.
- tamperproof security paper further comprises calcium carbonate or / and sodium carbonate at least 0.1% by dry weight relative to the dry weight of paper.
- tamperproof security paper made with barium carbonate is non-fluorescent under lighting in the field of ultraviolet radiation, which is a very important feature in the field considered, and has a whiteness according to ISO 2470-1. at least 75.
- the tamperproof security paper according to the invention is very stable with respect to the oxidation of air and with respect to variations in climatic conditions which is also quite particular compared with the papers sold in the field whose stability is very bad. Which poor stability results in a loss of whiteness over time and a corresponding loss of reactivity compared to the erasers used by forgers.
- tamperproof security paper has a loss of whiteness according to ISO 2470-1 after one month of exposure to the open air under standard conditions of temperature, 23 ° C, and hygrometry , 50%, less than 5% of the value measured at the time of paper manufacture.
- tamperproof security paper further comprises a cobalt or nickel carbonate at a maximum rate of 5% by dry weight relative to the dry weight of paper.
- tamperproof security paper may further comprise a reagent with respect to acids or / and agents capable of reacting with non-aqueous solvents by developing a colored reaction.
- reagents are known in the field of security papers.
- the barium carbonate can be introduced through the surface, coating or any surface coating.
- the tamperproof security paper may contain barium carbonate located in a surface coating, advantageously this barium carbonate is present in a proportion of at least 5% by dry weight of said coating, which coating containing at least one binder capable of maintaining the cohesion of the surface deposit.
- Binders capable of maintaining surface cohesion are known in the field, they may be latex, starch, polyvinyl alcohols and any type of polymer conventionally known in the coating field to maintain the cohesion of the surface. layer.
- the amount of layer deposited on the paper containing barium carbonate can be chosen in a wide range between 0.5 g / m 2 and more than 10 g / m 2 depending on the type of security document falsifiable to achieve.
- the formed, tamper-evident security paper is non-fluorescent and advantageously comprises calcium carbonate and / or sodium at least 5% by dry weight relative to the dry weight of the surface coating.
- Tamper-resistant test paper of 95 g / m 2 made from a paper pulp having 5% dry weight, based on dry fiber, of barium carbonate in the form of a powder introduced into the pulper at the time of pulping said dry fibers. It is further introduced into the paper 5% by dry weight relative to the weight of calcium carbonate fibers.
- the paper is mass-bonded with a dimeric alkyl ketene and the amount of sulfate-containing components fed by the paste and the various additives introduced into the paper is less than 1% by dry weight based on the weight of paper manufactured.
- the paper is pasted in size-press with a starch solution.
- the paper is reactive in pink / purple with the following redox combination applied in two steps: 1) application of an aqueous solution comprising 5% by weight potassium permanganate mixed with 1% sulfuric acid,
- the non-fluorescent paper thus manufactured has a whiteness measured at 80 according to ISO 2470-1, which is very high compared to the usual security papers.
- the whiteness of the formed paper evolves almost no time, there is less than 1% loss of whiteness compared to the initial value measured at the time of manufacture, after a storage time of one month under the standard standardized conditions of 50% relative humidity and 23 ° C.
- Tamper-resistant paper of a grammage of 90 g / m 2 for use as a gift voucher comprising personalization, made with a paste comprising 5% by dry weight of calcium carbonate relative to the dry paste and surface-coated in size-press with a composition comprising, in percentage with respect to the bath weight of barium carbonate at 8% and 1% of sodium carbonate, so as to retain in the finished paper of the order of 3% of dry barium carbonate relative to the dry weight of paper and 0.4% of sodium carbonate.
- the size-press preparation further comprising a starch-type binder at a level of 12% dry relative to the weight of the preparation.
- the carrier paper has less than 1% by dry weight of sulfation or sulfite ion-yielding compounds based on the weight of dry paper and the size-press composition is free of such ions.
- the tamperproof paper for check described in Example 1 is made under the same conditions for the production of the support containing barium carbonate, the dry quantity being provided at height. of 3% based on the weight of fibers and 10% by weight of calcium carbonate is added, the paper contains less than 0.5% by weight of components bringing sulphate or sulphite ions into the paper. Water-insoluble dyes which are soluble in non-aqueous solvents are added to the dough so as to render the paper tamper-proof with respect to the solvents.
- cobalt carbonate pre-dispersed in water at a rate of 2% by dry weight relative to the bath weight, which corresponds substantially to 0.8% by dry weight relative to the weight of finished paper .
- the wet load to the size-press being of the order of 40% relative to the dry weight of the support paper.
- the paper is also reactive with solvents, with bleach and strong bases, developing color reactions easily noticeable to the naked eye.
- 60 g / m 2 security paper comprising a non-fluorescent support loaded with 10% by weight of calcium carbonate relative to the total weight of the paper, coated off the paper machine with a composition comprising barium carbonate and a latex styrene butadiene carboxylated so as to deposit a dry layer of 10 g / m 2 with 4 g / m 2 of barium carbonate, or 40% of the dry weight deposited on the surface of the paper.
- the layer is provided free of components capable of bringing sulphite or sulphate ions into the preparation and the support paper contains less than 3% by dry weight relative to the weight of paper of said components.
- the paper thus manufactured is irreversible in relation to permanganate-based redox combinations irreversibly, in the same manner as in the preceding examples.
- the coloration formed between the paper and the redox-reducing combinations may change over time to form a beige, orange or brown coloration depending on the conditions of the tests, depending on the concentrations of the oxidizing and reducing solutions.
- the reducing agents used according to the reagents or additives included in the paper and in the manner of applying the redox combinations to the paper. All these colors, however, are irreversible compared to the addition of an erasing agent that can be applied later.
- paper should be understood as a flexible porous network, advantageously fibrous, printable and usable for making secure documents, it is preferably a paper machine paper, but the term also encompasses nonwoven products that can be made by a non-papermaking route and the cardboard type materials or various fibrous agglomerates made in one or more jets.
- the invention also relates more generally to all security documents incorporating paper and which comprise variable data that can be modified by falsification, according to the invention the documents protected against forgery by means of redox combinations.
- permanganate are characterized in that they incorporate barium carbonate and comprise a maximum level of sulphite or sulphate ions of 3% relative to the weight of the document.
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Abstract
The present invention relates to a security paper that is unfalsifiable with respect to attempts at falsification with redox combinations based on permanganate, characterized in that it comprises, on its surface or/and in its bulk, barium carbonate and in that it is manufactured with compounds that introduce less than 3% by dry weight relative to the dry weight of paper of salts comprising sulphate or sulphite ions.
Description
PAPIER DE SECURITE INFALSIFIABLE AUX AGENTS OXYDO- SAFETY PAPER INFALSIFIABLE TO OXYDO AGENTS
REDUCTEURS REDUCING
L'invention concerne un papier de sécurité infalsifiable vis-à-vis des agents oxydo-réducteurs. Les documents tels que les chèques, les vouchers, les passeports, certains bons cadeaux, les documents d'identité et divers papiers tels que les ordonnances médicales, les titres de propriété et divers documents d'état civil contiennent des informations personnalisées susceptibles d'être modifiées par des faussaires. Les modifications consistent à employer des agents d'effacement pour enlever les données variables des documents et apposer de nouvelles informations, un nouveau destinataire ou un autre montant sur un chèque, par exemple. The invention relates to a tamper-resistant security paper vis-à-vis oxidation-reducing agents. Documents such as checks, vouchers, passports, certain gift vouchers, identity documents and other documents such as medical prescriptions, title deeds and other vital documents contain personalized information that may be modified by counterfeiters. The changes involve using clearing agents to remove variable data from documents and to post new information, a new recipient, or another amount on a check, for example.
Les agents d'effacement utilisés par les faussaires sont tous ceux susceptibles d'être trouvés dans le commerce, il est notamment employé l'eau de javel, des acides, des bases, des combinaisons oxydo-réductrices, des solvants et de manière très générale tous les produits susceptibles d'effacer les encres tels que par exemple des laques à cheveux, du white spirit, le liquide de frein, des détachants liquides, etc .. Parmi les produits infalsifiables connus il peut notamment être cité ceux décrits dans le brevet FR 2 650 606 qui permettent un traitement des papiers vis-à-vis des bases, des crayons effaceurs et des agents réducteurs alcalins ou le brevet EP 190 087 qui indique plus spécifiquement des réactifs pour les crayons effaceurs. Le document EP 494 828 indique une réaction d'infalsifiabilité vis-à-vis du sulfite de sodium. Des réactifs vis-à-vis des acides sont connus depuis de très nombreuses années, par exemple par le document US 322 130 en date du 14 juillet 1885 ou US 643 084 de l'année 1900. The erasing agents used by counterfeiters are all those likely to be found commercially, it is particularly used bleach, acids, bases, redox combinations, solvents and very generally all the products capable of erasing inks such as for example hairsprays, white spirit, brake fluid, liquid stain removers, etc. Among the known tamper-proof products it may especially be mentioned those described in the patent FR 2,650,606 which allow a paper treatment vis-à-vis bases, erasers and alkaline reducing agents or EP 190 087 which more specifically indicates reagents for erasers. EP 494 828 indicates an infalsifiability reaction with respect to sodium sulfite. Acid reactants have been known for many, many years, for example, US 322,130 dated July 14, 1885 or US 643,084 of the year 1900.
Des réactions d'infalsifiabilité vis-à-vis des combinaisons oxydo-réductrices sont connues par les documents US 4 478 681 , EP 174 885 ou EP 378 029, ces solutions présentent cependant toutes des défauts importants, notamment en ce qui concerne la toxicité des produits chimiques employés ou l'instabilité des réactifs vis à vis de l'oxydation due à l'air, ce qui entraîne un vieillissement du papier, lequel se traduit par une perte significative de blancheur et de réactivité. Tamper reactions with respect to the redox combinations are known from documents US Pat. No. 4,478,681, EP 174,885 and EP 378,029, all of these solutions, however, have important defects, in particular as regards the toxicity of the compounds. the chemicals used or the instability of the reagents with respect to air oxidation, resulting in paper aging, which results in a significant loss of whiteness and reactivity.
Le problème critique qui se pose aujourd'hui pour les papiers de sécurité infalsifiables est d'obtenir des papiers qui soient "durablement blancs et
réactifs et qui ne présentent pas de toxicité significative pour les personnes ou pour l'environnement. The critical problem today for tamper-proof security papers is to obtain papers that are " permanently white and reagents and that do not present significant toxicity to people or the environment.
Le papier infalsifiable selon l'invention vise à répondre à cette problématique pour les réactions infalsifiables vis à vis des combinaisons oxydo-réductrices basées sur l'emploi du permanganate comme agent oxydant. The tamperproof paper according to the invention aims to respond to this problem for tamper-resistant reactions with respect to redox combinations based on the use of permanganate as an oxidizing agent.
Ainsi le papier de sécurité infalsifiable vis-à-vis des tentatives de falsification avec des combinaisons oxydo-réductrices à base de permanganate est caractérisé en ce qu'il comporte sur sa surface ou/et dans sa masse du carbonate de baryum, et en ce qu'il est fabriqué avec des composants introduisant moins de 3% en poids sec par rapport au poids sec de papier des sels comportant des ions sulfates ou sulfites. Thus tamperproof security paper vis-à-vis tampering attempts with redox-based combinations based on permanganate is characterized in that it comprises on its surface and / or in its mass barium carbonate, and in that that it is manufactured with components introducing less than 3% by dry weight relative to the dry weight of paper of the salts comprising sulphate or sulphite ions.
Les avantages du papier de sécurité infalsifiable selon l'invention sont multiples : - le papier obtenu est très blanc et sa blancheur n'est pas altérée dans le temps puisque le carbonate de baryum est insensible à l'oxydation de l'air, par ailleurs le produit est non fluorescent ce qui est un avantage supplémentaire, The advantages of the tamperproof security paper according to the invention are multiple: the paper obtained is very white and its whiteness is not altered in time since the barium carbonate is insensitive to the oxidation of the air, moreover the product is non-fluorescent which is an added benefit,
- en raison de cette stabilité les réactions avec les agents d'effacement oxydo-réducteurs sont également stables dans le temps, contrairement à tous les autres papiers de sécurité dont la durée de vie est limitée, because of this stability, the reactions with the redox-reducing agents are also stable over time, unlike all the other security papers whose life is limited,
- en raison de sa nature légèrement alcaline le carbonate de baryum autorise la réalisation de papiers de sécurité en collage neutre, lequel est reconnu pour sa stabilité dans le temps, - Due to its slightly alkaline nature barium carbonate allows the realization of security papers in neutral bonding, which is recognized for its stability over time,
- en raison de ses caractéristiques physiques spécifiques le carbonate de baryum amène également de l'opacité au papier sans qu'il soit nécessaire d'ajouter une charge telle que l'oxyde de titane pour cela, cela se traduit de fait par une économie de matière et un prix de revient du papier plus bas, - Because of its specific physical characteristics barium carbonate also brings opacity to paper without the need to add a charge such as titanium oxide for this, this actually results in a saving of material and a lower cost price of paper,
- enfin le produit n'est pas toxique et n'a pas d'impact fort sur les personnes ou sur l'environnement, son emploi ne nécessite pas des précautions particulières, contrairement aux autres réactifs employés usuellement dans les papiers de sécurité. D'autres caractéristiques et avantages de l'invention se dégageront de la description qui va suivre.
L'invention concerne un papier traité dans sa masse ou à sa surface avec du carbonate de baryum pour être infalsifiable vis-à-vis des agents d'effacement comportant des combinaisons oxydo-réductrices basées sur le permanganate de potassium comme agent oxydant. De telles combinaisons en vue d'effacer des données variables sur les documents, manuscrites ou imprimées, concernent par exemple : - Finally the product is not toxic and has no impact on people or the environment, its use does not require special precautions, unlike other reagents usually used in security papers. Other features and advantages of the invention will emerge from the description which follows. The invention relates to a paper treated in its mass or on its surface with barium carbonate to be unfalsifiable vis-à-vis erasing agents comprising oxido-reducing combinations based on potassium permanganate as an oxidizing agent. Such combinations in order to erase variable data on documents, written or printed, concern for example:
- l'application d'un mélange de permanganate de potassium en milieu acidifié, puis l'application de bisulfite de sodium comme réducteur, the application of a mixture of potassium permanganate in an acidified medium, then the application of sodium bisulfite as a reducing agent,
- l'application de permanganate de potassium, puis l'application de bisulfite de sodium comme réducteur. - the application of potassium permanganate, then the application of sodium bisulfite as reducing agent.
L'invention a également pour objectif de traiter le papier de manière à ce que les combinaisons oxydo-réductrices à base de permanganate appliquées par les faussaires conduisent à une coloration du papier qui soit définitive, irréversible, le papier une fois coloré par une combinaison telle que précédemment décrite ne peut plus être décoloré par l'application d'un autre agent chimique, en cela la réaction infalsifiable est tout à fait intéressante et originale. The invention also aims to treat the paper so that the redox-based combinations of permanganate applied by the forgers lead to a coloring of the paper which is definitive, irreversible, the paper once colored by a combination such that previously described can not be discolored by the application of another chemical agent, in this the tamper-proof reaction is quite interesting and original.
Afin que la réaction colorée en présence de la combinaison oxydo-réductrice puisse se développer il est indispensable que le papier comporte le moins possible d'ions sulfate ou sulfites ou de composés susceptibles de transformer le carbonate de baryum en sulfate de baryum, lequel est inactif vis à vis desdits agents d'effacement. So that the color reaction in the presence of the redox combination can develop it is essential that the paper has the least possible sulphate or sulphite ions or compounds capable of converting barium carbonate to barium sulfate, which is inactive with respect to said erasing agents.
De tels ions sont traditionnellement amenés dans le papier par le sulfate d'alumine qui est indispensable au développement du collage du papier en milieu acide, le papier doit donc être collé en milieu dit "neutre" ou "pseudoneutre" dans le jargon papetier, c'est à dire collé sans le mélange colophane - sulfate d'alumine. Such ions are traditionally brought into the paper by the sulphate of alumina which is essential for the development of the paper gluing in an acid medium, the paper must therefore be glued in a so-called "neutral" or "pseudoneutre" medium in the jargon paper, c ie, pasted without the rosin-alumina sulphate mixture.
Une autre source d'ions sulfate dans les papiers de sécurité provient de l'adjonction de sulfate de manganèse, de sulfate de cuivre, de sulfate de cobalt ou de composés amenant des sels comportant de tels ions dans le papier, ces produits sont notamment utilisés pour amener une réaction colorée vis à vis de tentatives d'effacement avec de l'eau de javel, les agents alcalins et les acides. Pour tourner la difficulté et obtenir les réactions souhaitées il est prévu d'utiliser dans le papier du chlorure de manganèse ou d'autres composants qui développent les mêmes réactions connues sans apport d'ions sulfate, selon une autre variante des composants organiques peuvent aussi se substituer à ces réactifs minéraux.
Le papier dans lequel est introduit le réactif infaisifiabie vis à vis des combinaisons oxydo-réductrices est donc tout à fait particulier par sa composition qui doit contenir le moins possible d'ions sulfate ou sulfite dans sa composition et cela tout le long de sa préparation. Idéalement le papier devrait être exempt de tels ions mais en pratique ce n'est pas possible et une quantité minimale est malgré tout tolérable. Another source of sulphate ions in the security papers comes from the addition of manganese sulphate, copper sulphate, cobalt sulphate or compounds bringing salts containing such ions in the paper, these products are especially used. to bring a color reaction against erasing attempts with bleach, alkalis and acids. In order to turn the difficulty and obtain the desired reactions, it is intended to use in the paper manganese chloride or other components which develop the same known reactions without the addition of sulfate ions, according to another variant of the organic components can also be used. substitute for these mineral reagents. The paper in which the infeasible reagent is introduced with respect to the redox combinations is therefore quite particular in its composition which must contain as little sulphate or sulphite ions in its composition and that all along its preparation. Ideally the paper should be free of such ions but in practice this is not possible and a minimal amount is still tolerable.
Ainsi selon l'invention le papier de sécurité infaisifiabie vis-à-vis des tentatives de falsification avec des combinaisons oxydo-réductrices à base de permanganate est caractérisé en ce qu'il comporte sur sa surface et/ou dans sa masse du carbonate de baryum et en ce qu'il est fabriqué avec des composants introduisant moins de 3% en poids sec par rapport au poids sec de papier des sels comportant des ions sulfates ou sulfites. Thus, according to the invention, the infeasible security paper with respect to the attempts of falsification with redox-based combinations based on permanganate is characterized in that it comprises on its surface and / or in its mass barium carbonate. and in that it is manufactured with components introducing less than 3% by dry weight, based on the dry weight of paper, of salts comprising sulphate or sulphite ions.
Avantageusement le papier de sécurité infaisifiabie comporte au moins 1% et au maximum 20% de carbonate de baryum en poids sec par rapport au poids sec dudit papier de sécurité. Advantageously, the infeasible security paper comprises at least 1% and at most 20% of barium carbonate by dry weight relative to the dry weight of said security paper.
Plus préférentiellement encore, le papier de sécurité infaisifiabie comporte entre 2% et 10% de carbonate de baryum en poids sec par rapport au poids sec dudit papier de sécurité et est fabriqué avec des composants introduisant moins de 1% en poids sec par rapport au poids sec de papier des sels comportant des ions sulfates ou sulfites. More preferably still, the infeasible security paper comprises between 2% and 10% of barium carbonate by dry weight relative to the dry weight of said security paper and is manufactured with components introducing less than 1% by dry weight relative to the weight. dry paper salts containing sulphate or sulphite ions.
La quantité de carbonate de baryum à introduire dans le papier dépend du niveau de coloration souhaité pour la réaction infaisifiabie et de la quantité d'ions sulfites ou sulfates présents lors de la fabrication du papier. Si de tels poisons sont présents en quantité notable, soit par apport dans la pâte à papier, soit par introduction à la size-press, soit par introduction par un traitement de surface ultérieur du papier, par exemple par couchage ou par un vernissage, la quantité à introduire de carbonate de baryum devra être adaptée et plus élevée que si ces ions sont absents. The amount of barium carbonate to be introduced into the paper depends on the level of coloration desired for the infeasible reaction and the amount of sulfite or sulphate ions present in the papermaking process. If such poisons are present in a significant amount, either by input into the pulp, or by introduction to the size-press, or by introduction by a subsequent surface treatment of the paper, for example by coating or by varnishing, the The amount to be introduced of barium carbonate will have to be adapted and higher than if these ions are absent.
Le carbonate de baryum est avantageusement introduit dans le papier au moment de la préparation de la pâte, par exemple dans le pulpeur ou dans le procédé traditionnel d'introduction de la charge de masse. Le carbonate de baryum peut être introduit sous forme de poudre, d'un "slurry" qui est une poudre dispersée dans de l'eau, ou fabriqué in-situ par un mélange de carbonate de sodium en présence d'un sel soluble de baryum. Une telle préparation réalisée in-situ dans la pâte à papier présente l'avantage d'un enrobage des fibres papetières par le carbonate de baryum avec une réactivité accrue par rapport aux réactions infalsifiables. The barium carbonate is advantageously introduced into the paper at the time of preparation of the dough, for example in the pulper or in the traditional method of introducing the mass load. The barium carbonate can be introduced in the form of a powder, a "slurry" which is a powder dispersed in water, or manufactured in-situ by a mixture of sodium carbonate in the presence of a soluble salt of barium . Such a preparation produced in situ in the paper pulp has the advantage of coating the paper fibers with barium carbonate with increased reactivity compared to tamper-resistant reactions.
Le carbonate de baryum peut aussi être introduit une fois que la pâte a été égouttée, par le size-press ou par un dispositif quelconque d'enduction placé
dans ou hors de la machine à papier, par un dispositif de couchage notamment, de manière à apporter le réactif à la surface du papier. The barium carbonate can also be introduced once the paste has been drained, by the size-press or by any coating device placed in or out of the paper machine, in particular by a coating device, so as to bring the reagent to the surface of the paper.
Lors de la mise au point du papier contenant le carbonate de baryum il a été trouvé avantageux d'introduire des réactifs et des additifs pour renforcer la réactivité, la blancheur ou la stabilité du papier. In developing the paper containing the barium carbonate it has been found advantageous to introduce reagents and additives to enhance the reactivity, whiteness or stability of the paper.
Selon l'invention le papier de sécurité infalsifiable comporte en outre du carbonate de calcium ou/et du carbonate de sodium à au moins 0.1 % en poids sec par rapport au poids sec de papier. According to the invention tamperproof security paper further comprises calcium carbonate or / and sodium carbonate at least 0.1% by dry weight relative to the dry weight of paper.
Par ailleurs le papier de sécurité infalsifiable fabriqué avec du carbonate de baryum est non fluorescent sous un éclairage dans le domaine du rayonnement ultraviolet, ce qui est une caractéristique très importante dans le domaine considéré, et présente une blancheur selon la norme ISO 2470-1 d'au moins 75. Furthermore tamperproof security paper made with barium carbonate is non-fluorescent under lighting in the field of ultraviolet radiation, which is a very important feature in the field considered, and has a whiteness according to ISO 2470-1. at least 75.
Le papier de sécurité infalsifiable selon l'invention est très stable par rapport à l'oxydation de l'air et par rapport aux variations des conditions climatiques ce qui est également tout à fait particulier par rapport aux papiers commercialisés dans le domaine dont la stabilité est très mauvaise. Laquelle mauvaise stabilité se traduit par une perte de blancheur au cours du temps et une perte corrélative de réactivité par rapport aux agents d'effacement utilisés par les faussaires. The tamperproof security paper according to the invention is very stable with respect to the oxidation of air and with respect to variations in climatic conditions which is also quite particular compared with the papers sold in the field whose stability is very bad. Which poor stability results in a loss of whiteness over time and a corresponding loss of reactivity compared to the erasers used by forgers.
Ainsi selon l'invention le papier de sécurité infalsifiable dispose d'une perte de blancheur selon la norme ISO 2470-1 après un mois d'exposition à l'air libre dans des conditions normalisées de température, 23°C, et d'hygrométrie, 50%, de moins de 5% par rapport à la valeur mesurée au moment de la fabrication du papier. Thus according to the invention tamperproof security paper has a loss of whiteness according to ISO 2470-1 after one month of exposure to the open air under standard conditions of temperature, 23 ° C, and hygrometry , 50%, less than 5% of the value measured at the time of paper manufacture.
Afin de réaliser un papier infalsifiable apte à réagir avec de nombreux agents différents d'effacement l'homme de l'art peut être amené à ajouter au papier des réactifs complémentaires, pour apporter par exemple une réaction vis à vis de l'eau de javel, des bases, des acides ou des solvants. Il a été trouvé avantageux dans cette option d'introduire des réactifs spécifiquement sélectionnés pour la compatibilité avec le carbonate de baryum. In order to produce a tamper-resistant paper that is capable of reacting with many different erasing agents, those skilled in the art may be led to add complementary reagents to the paper, for example to provide a reaction with regard to bleach. , bases, acids or solvents. It has been found advantageous in this option to introduce reagents specifically selected for compatibility with barium carbonate.
Selon l'invention le papier de sécurité infalsifiable comporte en outre un carbonate de cobalt ou de nickel à un taux maximum de 5% en poids sec par rapport au poids sec de papier. Selon l'invention le papier de sécurité infalsifiable peut comporter en outre un réactif vis à vis des acides ou/et des agents susceptibles de réagir avec les solvants non aqueux en développant une réaction colorée. De tels réactifs sont connus dans le domaine des papiers de sécurité.
Tel que cela a été précédemment indiqué le carbonate de baryum peut être introduit par la surface, par un couchage ou un revêtement quelconque de surface. According to the invention tamperproof security paper further comprises a cobalt or nickel carbonate at a maximum rate of 5% by dry weight relative to the dry weight of paper. According to the invention tamperproof security paper may further comprise a reagent with respect to acids or / and agents capable of reacting with non-aqueous solvents by developing a colored reaction. Such reagents are known in the field of security papers. As previously indicated, the barium carbonate can be introduced through the surface, coating or any surface coating.
Ainsi selon l'invention le papier de sécurité infalsifiable peut contenir du carbonate de baryum localisé dans un revêtement de surface, avantageusement ce carbonate de baryum est présent à raison d'au moins 5% en poids sec dudit revêtement, lequel revêtement contenant au moins un liant apte à maintenir la cohésion du dépôt de surface. Thus, according to the invention, the tamperproof security paper may contain barium carbonate located in a surface coating, advantageously this barium carbonate is present in a proportion of at least 5% by dry weight of said coating, which coating containing at least one binder capable of maintaining the cohesion of the surface deposit.
Les liants aptes à maintenir la cohésion de surface sont connus dans le domaine, il peut s'agir de latex, d'amidon, d'alcools polyvinyliques et de tout type de polymère classiquement connu dans le domaine du couchage pour maintenir la cohésion de la couche. Binders capable of maintaining surface cohesion are known in the field, they may be latex, starch, polyvinyl alcohols and any type of polymer conventionally known in the coating field to maintain the cohesion of the surface. layer.
La quantité de couche déposée sur le papier contenant du carbonate de baryum peut être choisie dans une large plage entre 0.5 g/m2 et plus de 10 g/m2 selon le type de document de sécurité infalsifiable à réaliser. The amount of layer deposited on the paper containing barium carbonate can be chosen in a wide range between 0.5 g / m 2 and more than 10 g / m 2 depending on the type of security document falsifiable to achieve.
Selon l'invention le papier de sécurité infalsifiable couché formé est non fluorescent et comporte avantageusement du carbonate de calcium ou/et de sodium à au moins 5% en poids sec par rapport au poids sec du revêtement de surface. According to the invention, the formed, tamper-evident security paper is non-fluorescent and advantageously comprises calcium carbonate and / or sodium at least 5% by dry weight relative to the dry weight of the surface coating.
Des exemples avantageux de réalisation de l'invention indiqués ci-après illustrent l'invention. Examples of advantageous embodiments of the invention indicated below illustrate the invention.
Exemple 1 : Example 1
Papier infalsifiable à usage de chèque d'un grammage de 95 g/m2 fabriqué avec une pâte à papier comportant en poids sec 5%, par rapport aux fibres sèches, de carbonate de baryum sous forme de poudre introduite dans le pulpeur au moment de la mise en pâte desdites fibres sèches. Il est introduit en outre dans le papier 5% en poids sec par rapport au poids de fibres du carbonate de calcium. Tamper-resistant test paper of 95 g / m 2 made from a paper pulp having 5% dry weight, based on dry fiber, of barium carbonate in the form of a powder introduced into the pulper at the time of pulping said dry fibers. It is further introduced into the paper 5% by dry weight relative to the weight of calcium carbonate fibers.
Le papier est collé en masse avec un alkyl cétène dimère et la quantité de composants contenant des ions sulfate amenée par la pâte et les additifs divers introduits dans le papier est inférieure à 1% en poids sec par rapport au poids de papier fabriqué. The paper is mass-bonded with a dimeric alkyl ketene and the amount of sulfate-containing components fed by the paste and the various additives introduced into the paper is less than 1% by dry weight based on the weight of paper manufactured.
Le papier est encollé en size-press avec une solution d'amidon. The paper is pasted in size-press with a starch solution.
Ainsi fabriqué le papier est réactif en rose/violet avec la combinaison oxydo- réductrice suivante appliquée en deux étapes :
1 ) application d'une solution aqueuse comportant du permanganate de potassium à 5% en poids mélangé avec de l'acide sulfurique à 1 %, Thus manufactured the paper is reactive in pink / purple with the following redox combination applied in two steps: 1) application of an aqueous solution comprising 5% by weight potassium permanganate mixed with 1% sulfuric acid,
2) application d'une solution saturée de bisulfite de sodium dans l'eau. 2) application of a saturated solution of sodium bisulfite in water.
La coloration développée avec ce mélange est irréversible par rapport à l'action d'autres agents d'effacement ajoutés ultérieurement. The coloration developed with this mixture is irreversible with respect to the action of other erasing agents subsequently added.
Le papier non fluorescent ainsi fabriqué comporte une blancheur mesurée à 80 selon la norme ISO 2470-1 , très élevée par rapport aux papiers de sécurité usuels. La blancheur du papier formé évolue quasiment pas dans le temps, il est constaté moins de 1 % de perte de blancheur par rapport à la valeur initiale mesurée au moment de la fabrication, après un temps de stockage de un mois dans les conditions standardisées usuelles de 50% d'humidité relative et de 23°C. The non-fluorescent paper thus manufactured has a whiteness measured at 80 according to ISO 2470-1, which is very high compared to the usual security papers. The whiteness of the formed paper evolves almost no time, there is less than 1% loss of whiteness compared to the initial value measured at the time of manufacture, after a storage time of one month under the standard standardized conditions of 50% relative humidity and 23 ° C.
Exemple 2 : Example 2
Papier infalsifiable d'un grammage de 90 g/m2 à usage de bon cadeau, comportant une personnalisation, fabriqué avec une pâte comportant 5% en poids sec de carbonate de calcium par rapport à la pâte sèche et enduit en surface en size-press avec une composition comportant en pourcentage par rapport au poids de bain du carbonate de baryum à hauteur de 8% et 1 % de carbonate de sodium, de manière à retenir dans le papier fini de l'ordre de 3% de carbonate de baryum en sec par rapport au poids sec de papier et 0.4% de carbonate de sodium. La préparation en size-press comportant en outre un liant de type amidon à hauteur de 12% en sec par rapport au poids de préparation. Tamper-resistant paper of a grammage of 90 g / m 2 for use as a gift voucher, comprising personalization, made with a paste comprising 5% by dry weight of calcium carbonate relative to the dry paste and surface-coated in size-press with a composition comprising, in percentage with respect to the bath weight of barium carbonate at 8% and 1% of sodium carbonate, so as to retain in the finished paper of the order of 3% of dry barium carbonate relative to the dry weight of paper and 0.4% of sodium carbonate. The size-press preparation further comprising a starch-type binder at a level of 12% dry relative to the weight of the preparation.
Le papier support comporte moins de 1 % en poids sec de composés amenant des ions sulfates ou sulfites par rapport au poids de papier sec et la composition en size-press est exempte de tels ions. The carrier paper has less than 1% by dry weight of sulfation or sulfite ion-yielding compounds based on the weight of dry paper and the size-press composition is free of such ions.
Ainsi fabriqué le papier est réactif en rose/violet avec la combinaison oxydo- réductrice suivante appliquée en deux étapes : Thus manufactured the paper is reactive in pink / purple with the following redox combination applied in two steps:
1 ) application d'une solution aqueuse comportant du permanganate de potassium à 5% en poids, 1) application of an aqueous solution comprising potassium permanganate at 5% by weight,
2) application d'une solution saturée de bisulfite de sodium dans l'eau. Exemple 3 2) application of a saturated solution of sodium bisulfite in water. Example 3
Le papier infalsifiable pour chèque décrit dans l'exemple 1 est réalisé dans les mêmes conditions pour ce qui consiste la fabrication du support contenant du carbonate de baryum, la quantité sèche étant prévue à hauteur
de 3% par rapport au poids de fibres et il est ajouté 10% en poids de carbonate de calcium, le papier contient moins de 0.5% en poids de composants amenant des ions sulfates ou sulfites dans le papier. Il est ajouté dans la pâte des colorants insolubles dans l'eau mais solubles dans les solvants non aqueux de manière à rendre le papier infalsifiable vis à vis des solvants. The tamperproof paper for check described in Example 1 is made under the same conditions for the production of the support containing barium carbonate, the dry quantity being provided at height. of 3% based on the weight of fibers and 10% by weight of calcium carbonate is added, the paper contains less than 0.5% by weight of components bringing sulphate or sulphite ions into the paper. Water-insoluble dyes which are soluble in non-aqueous solvents are added to the dough so as to render the paper tamper-proof with respect to the solvents.
A la presse encolleuse il est ajouté du carbonate de cobalt pré-dispersé dans l'eau à raison de 2% en poids sec par rapport au poids de bain, ce qui correspond sensiblement à 0.8 % en poids sec par rapport au poids de papier fini. L'emport humide à la size-press étant de l'ordre de 40% par rapport au poids sec de papier support. To the sizing press is added cobalt carbonate pre-dispersed in water at a rate of 2% by dry weight relative to the bath weight, which corresponds substantially to 0.8% by dry weight relative to the weight of finished paper . The wet load to the size-press being of the order of 40% relative to the dry weight of the support paper.
Ainsi fabriqué le papier est réactif en rose/violet avec la combinaison oxydo- réductrice suivante appliquée en deux étapes : Thus manufactured the paper is reactive in pink / purple with the following redox combination applied in two steps:
1) application d'une solution aqueuse comportant du permanganate de potassium à 5% en poids mélangé avec de l'acide sulfurique à 1%, 1) application of an aqueous solution comprising 5% by weight potassium permanganate mixed with 1% sulfuric acid,
2) application d'une solution saturée de bisulfite de sodium dans l'eau.2) application of a saturated solution of sodium bisulfite in water.
Le papier est de plus réactif avec les solvants, avec l'eau de javel et les bases fortes en développant des réactions colorées aisément perceptibles à l'oeil nu. The paper is also reactive with solvents, with bleach and strong bases, developing color reactions easily noticeable to the naked eye.
Le papier ainsi fabriqué est non fluorescent sous un éclairage UV à 365nm. Exemple 4 : The paper thus manufactured is non-fluorescent under UV illumination at 365 nm. Example 4
Papier de sécurité de 60 g/m2 comportant un support non fluorescent chargé avec du carbonate de calcium à hauteur de 10% en poids par rapport au poids total du papier, couché hors machine à papier avec une composition comportant du carbonate de baryum et un latex styrène butadiène carboxylé de manière à déposer une couche sèche de 10 g/m2 comportant 4 g/m2 de carbonate de baryum, soit 40% du poids sec déposé à la surface du papier. La couche est prévue exempte de composants susceptibles d'amener des ions sulfites ou sulfates dans la préparation et le papier support contient moins de 3% en poids sec par rapport au poids de papier desdits composants. 60 g / m 2 security paper comprising a non-fluorescent support loaded with 10% by weight of calcium carbonate relative to the total weight of the paper, coated off the paper machine with a composition comprising barium carbonate and a latex styrene butadiene carboxylated so as to deposit a dry layer of 10 g / m 2 with 4 g / m 2 of barium carbonate, or 40% of the dry weight deposited on the surface of the paper. The layer is provided free of components capable of bringing sulphite or sulphate ions into the preparation and the support paper contains less than 3% by dry weight relative to the weight of paper of said components.
Ainsi fabriqué le papier est réactif en rose/violet avec la combinaison oxydo- réductrice suivante appliquée en deux étapes : Thus manufactured the paper is reactive in pink / purple with the following redox combination applied in two steps:
1) application d'une solution aqueuse comportant du permanganate de potassium à 5% en poids mélangé avec de l'acide sulfurique à 1%,
2) application d'une solution saturée de bisulfite de sodium dans l'eau. 1) application of an aqueous solution comprising 5% by weight potassium permanganate mixed with 1% sulfuric acid, 2) application of a saturated solution of sodium bisulfite in water.
Le papier ainsi fabriqué est infalsifiable vis à vis des combinaisons oxydo- réductrices à base de permanganate, de manière irréversible, de la même manière que dans les exemples précédents. Dans les quatre exemples précédents il est à noter que la coloration formée entre le papier et les combinaisons oxydo-réductrices peut évoluer dans le temps pour former une coloration beige, orange ou brune selon les conditions des tests, selon les concentrations des solutions oxydantes et réductrices, selon les agents réducteurs employés, selon les réactifs ou additifs inclus dans le papier et selon la manière d'appliquer les combinaisons oxydo- réductrices sur le papier. Toutes ces colorations sont toutefois irréversibles par rapport à l'ajout d'un agent d'effacement susceptible d'être appliqué ultérieurement. The paper thus manufactured is irreversible in relation to permanganate-based redox combinations irreversibly, in the same manner as in the preceding examples. In the four previous examples, it should be noted that the coloration formed between the paper and the redox-reducing combinations may change over time to form a beige, orange or brown coloration depending on the conditions of the tests, depending on the concentrations of the oxidizing and reducing solutions. according to the reducing agents used, according to the reagents or additives included in the paper and in the manner of applying the redox combinations to the paper. All these colors, however, are irreversible compared to the addition of an erasing agent that can be applied later.
Dans toute la description qui précède le terme papier doit être compris comme un réseau poreux flexible, avantageusement fibreux, imprimable et utilisable pour réaliser des documents sécurisés, il s'agit de préférence d'un papier réalisable sur machine à papier mais le terme englobe également les produits non tissés pouvant être réalisés par une voie non papetière et les matériaux de type carton ou des agglomérés fibreux variés réalisés en un ou plusieurs jets. Throughout the foregoing description, the term paper should be understood as a flexible porous network, advantageously fibrous, printable and usable for making secure documents, it is preferably a paper machine paper, but the term also encompasses nonwoven products that can be made by a non-papermaking route and the cardboard type materials or various fibrous agglomerates made in one or more jets.
L'invention est également relative de manière plus générale à tous les documents de sécurité incorporant du papier et qui comportent des données variables susceptibles d'être modifiées par falsification, selon l'invention les documents protégés contre la falsification au moyen de combinaisons oxydo- réductrices à base de permanganate sont caractérisés en ce qu'ils incorporent du carbonate de baryum et comportent un taux maximal d'ions sulfites ou sulfates de 3% par rapport au poids du document. The invention also relates more generally to all security documents incorporating paper and which comprise variable data that can be modified by falsification, according to the invention the documents protected against forgery by means of redox combinations. based on permanganate are characterized in that they incorporate barium carbonate and comprise a maximum level of sulphite or sulphate ions of 3% relative to the weight of the document.
Bien entendu, l'invention n'est pas limitée aux modes de réalisation décrits et représentés à titre d'exemples, mais elle comprend aussi tous les équivalents techniques ainsi que leurs combinaisons.
Of course, the invention is not limited to the embodiments described and represented by way of examples, but it also includes all the technical equivalents as well as their combinations.
Claims
REVENDICATIONS
1- Papier de sécurité infalsifiable vis-à-vis des tentatives de falsification avec des combinaisons oxydo-réductrices à base de permanganate, caractérisé en ce qu'il comporte sur sa surface ou/et dans sa masse du carbonate de baryum et en ce qu'il est fabriqué avec des composants introduisant moins de 3% en poids sec par rapport au poids sec de papier des sels comportant des ions sulfates ou sulfites. 1-tamperproof security paper vis-à-vis tampering attempts with redox combinations based on permanganate, characterized in that it comprises on its surface and / or in its mass of barium carbonate and in that It is manufactured with components introducing less than 3% dry weight based on the dry weight of paper of the salts comprising sulphate or sulphite ions.
2- Papier de sécurité infalsifiable selon la revendication 1 comportant au moins 1 % et au maximum 20% de carbonate de baryum en poids sec par rapport au poids sec dudit papier de sécurité. 2- tamperproof security paper according to claim 1 comprising at least 1% and at most 20% of barium carbonate by dry weight relative to the dry weight of said security paper.
3- Papier de sécurité infalsifiable selon la revendication 2 comportant entre 2% et 10% de carbonate de baryum en poids sec par rapport au poids sec dudit papier de sécurité et fabriqué avec des composants introduisant moins de 1 % en poids sec par rapport au poids sec de papier des sels comportant des ions sulfates ou sulfites. Tamper-proof security paper according to claim 2 comprising between 2% and 10% of barium carbonate by dry weight relative to the dry weight of said security paper and manufactured with components introducing less than 1% by dry weight relative to the weight. dry paper salts containing sulphate or sulphite ions.
4- Papier de sécurité infalsifiable selon la revendication 3 comportant en outre du carbonate de calcium ou/et du carbonate de sodium à au moins 0.1 % en poids sec par rapport au poids sec de papier. 5- Papier de sécurité infalsifiable selon la revendication 1 caractérisé en ce qu'il est non fluorescent sous un éclairage dans le domaine du rayonnement ultraviolet et qu'il présente une blancheur selon la norme ISO 2470-1 d'au moins 75. Tamperproof security paper according to claim 3 further comprising calcium carbonate and / or sodium carbonate at least 0.1% by dry weight relative to the dry weight of paper. 5 tamperproof security paper according to claim 1 characterized in that it is non-fluorescent under illumination in the field of ultraviolet radiation and has a whiteness according to ISO 2470-1 of at least 75.
6- Papier de sécurité infalsifiable selon la revendication 5 dont la perte de blancheur selon la norme ISO 2470-1 après un mois d'exposition à l'air libre dans des conditions normalisées de température, 23°C, et d'hygrométrie, 50%, est de moins de 5% par rapport à la valeur mesurée au moment de la fabrication dudit papier. 6 tamperproof security paper according to claim 5, the loss of whiteness according to ISO 2470-1 after one month of exposure to the open air under standard conditions of temperature, 23 ° C, and hygrometry, 50 %, is less than 5% with respect to the value measured at the time of manufacture of said paper.
7- Papier de sécurité infalsifiable selon la revendication 1 comportant en outre un carbonate de cobalt ou de nickel à un taux maximum de 5% en poids sec par rapport au poids sec de papier. 7 tamperproof security paper according to claim 1 further comprising a cobalt or nickel carbonate at a maximum rate of 5% by dry weight relative to the dry weight of paper.
8- Papier de sécurité infalsifiable selon la revendication 1 comportant en outre un réactif vis à vis des acides ou/et des agents susceptibles de réagir avec les solvants non aqueux en développant une réaction colorée.
9- Papier de sécurité infalsifiable selon la revendication 1 dans lequel le carbonate de baryum est localisé dans un revêtement de surface et présent à raison d'au moins 5% en poids sec dudit revêtement, lequel revêtement contenant au moins un liant apte à maintenir la cohésion du dépôt de surface. 8 tamperproof security paper according to claim 1 further comprising a reagent with respect to acids and / or agents capable of reacting with non-aqueous solvents by developing a color reaction. 9 tamperproof security paper according to claim 1 wherein the barium carbonate is located in a surface coating and present in an amount of at least 5% by dry weight of said coating, which coating containing at least one binder capable of maintaining the cohesion of the surface deposit.
10- Papier de sécurité infalsifiable selon la revendication 9 non fluorescent et comportant du carbonate de calcium ou/et de sodium à au moins 5% en poids sec par rapport au poids sec du revêtement de surface.
10 tamperproof security paper according to claim 9 non-fluorescent and comprising calcium carbonate and / or sodium at least 5% by dry weight relative to the dry weight of the surface coating.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR11/03261 | 2011-10-26 | ||
FR1103261A FR2981955B1 (en) | 2011-10-26 | 2011-10-26 | SAFETY PAPER INFALSIFIABLE TO OXYDO-REDUCING AGENTS |
Publications (1)
Publication Number | Publication Date |
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WO2013060947A1 true WO2013060947A1 (en) | 2013-05-02 |
Family
ID=47291086
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2012/000434 WO2013060947A1 (en) | 2011-10-26 | 2012-10-10 | Security paper that cannot be falsified using redox agents |
Country Status (2)
Country | Link |
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FR (1) | FR2981955B1 (en) |
WO (1) | WO2013060947A1 (en) |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US322130A (en) | 1885-07-14 | saxony | ||
US643084A (en) | 1898-09-08 | 1900-02-06 | Frederick H Schroder | Paper-making. |
US2378585A (en) * | 1936-12-23 | 1945-06-19 | Schroth Adolf | Safety paper |
US2702765A (en) * | 1951-10-20 | 1955-02-22 | Ncr Co | Method of sensitizing paper by forming salts therein |
US4478681A (en) | 1981-08-14 | 1984-10-23 | Bayer Aktiengesellschaft | Forgery-proof paper |
EP0174885A1 (en) | 1984-08-10 | 1986-03-19 | ARJOMARI-PRIOUX Société anonyme dite | Security paper and document against forgery by a chemical agent |
EP0190087A1 (en) | 1985-01-21 | 1986-08-06 | Aussedat-Rey | Forge-proof security paper, process for making a paper forge-proof and aqueous or organic composition especially useful in making a paper forge-proof |
EP0378029A2 (en) | 1988-12-07 | 1990-07-18 | Aussedat-Rey | Non-forgeable and non-fluorescent security paper, and document obtained |
FR2650606A1 (en) | 1989-08-07 | 1991-02-08 | Aussedat Rey | INFALSIFIABLE SAFETY PAPER AND USEFUL AQUEOUS OR ORGANIC COMPOSITION, IN PARTICULAR FOR MAKING INFALSIFIABLE PAPER |
EP0494828A1 (en) | 1991-01-11 | 1992-07-15 | Arjo Wiggins S.A. | Safety document |
-
2011
- 2011-10-26 FR FR1103261A patent/FR2981955B1/en not_active Expired - Fee Related
-
2012
- 2012-10-10 WO PCT/FR2012/000434 patent/WO2013060947A1/en active Application Filing
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US322130A (en) | 1885-07-14 | saxony | ||
US643084A (en) | 1898-09-08 | 1900-02-06 | Frederick H Schroder | Paper-making. |
US2378585A (en) * | 1936-12-23 | 1945-06-19 | Schroth Adolf | Safety paper |
US2702765A (en) * | 1951-10-20 | 1955-02-22 | Ncr Co | Method of sensitizing paper by forming salts therein |
US4478681A (en) | 1981-08-14 | 1984-10-23 | Bayer Aktiengesellschaft | Forgery-proof paper |
EP0174885A1 (en) | 1984-08-10 | 1986-03-19 | ARJOMARI-PRIOUX Société anonyme dite | Security paper and document against forgery by a chemical agent |
EP0190087A1 (en) | 1985-01-21 | 1986-08-06 | Aussedat-Rey | Forge-proof security paper, process for making a paper forge-proof and aqueous or organic composition especially useful in making a paper forge-proof |
EP0378029A2 (en) | 1988-12-07 | 1990-07-18 | Aussedat-Rey | Non-forgeable and non-fluorescent security paper, and document obtained |
FR2650606A1 (en) | 1989-08-07 | 1991-02-08 | Aussedat Rey | INFALSIFIABLE SAFETY PAPER AND USEFUL AQUEOUS OR ORGANIC COMPOSITION, IN PARTICULAR FOR MAKING INFALSIFIABLE PAPER |
EP0494828A1 (en) | 1991-01-11 | 1992-07-15 | Arjo Wiggins S.A. | Safety document |
Also Published As
Publication number | Publication date |
---|---|
FR2981955B1 (en) | 2013-11-01 |
FR2981955A1 (en) | 2013-05-03 |
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