EP0169750A1 - Luminescent security fibres; security documents and other materials containing these fibres - Google Patents

Luminescent security fibres; security documents and other materials containing these fibres Download PDF

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Publication number
EP0169750A1
EP0169750A1 EP85401148A EP85401148A EP0169750A1 EP 0169750 A1 EP0169750 A1 EP 0169750A1 EP 85401148 A EP85401148 A EP 85401148A EP 85401148 A EP85401148 A EP 85401148A EP 0169750 A1 EP0169750 A1 EP 0169750A1
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Prior art keywords
fibers
materials
dyeing
luminescent
security
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EP85401148A
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German (de)
French (fr)
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EP0169750B1 (en
EP0169750B2 (en
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Michel Jalon
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/29—Securities; Bank notes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/0004—General aspects of dyeing
    • D06P1/0012—Effecting dyeing to obtain luminescent or phosphorescent dyeings
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S283/00—Printed matter
    • Y10S283/903—Lottery ticket

Definitions

  • the present invention relates to security fibers, security threads, textile materials, plastic films and regenerated cellulose, plastic resins, luminescent, their production methods and their applications in fiduciary documents and other materials.
  • Security fibers are fibers that are incorporated into fiduciary documents or other matters for the purpose of ensuring identification, authentication, protection against counterfeiting, imitation or falsification.
  • the security threads are continuous threads or strips of film, introduced in the fiduciary documents for the same purpose as the safety fibers.
  • other materials designates here materials which, in order to fight against their counterfeiting, imitation or falsification require a means of identification, authentication and protection obtained by the incorporation of security fibers in or on these materials.
  • the present invention relates to the production of fibers preferably from the last group which are therefore invisible in sunlight or artificial light and which, under excitation of IR, UV or X rays, exhibit luminescence in one or more parts of the visible IR spectrum .
  • UV, or X IR, or X.
  • the dyes used in the context of this invention are Rare Earth compounds, or Lanthanides, with atomic number 57 to 71 to which are usually attached Yttrium and Thorium with atomic number 39 and 90 r Rare Earth compounds which have these luminescence characteristics and used in this invention are chelates.
  • the present invention therefore proposes to resolve these difficulties by describing a process for producing safety fibers in which the incorporation of lanthanide, Yttrium and Thorium chelates is done not in the spinning mass of continuous threads, but by a process for dyeing fibers already extruded and cut into fibers.
  • this invention has the advantage of having a certain similarity with the dyeing processes used by fiber dyers and therefore of using almost standard apparatuses in this industry, and of offering the possibility of carrying out manufacturing cycles compatible with the low quantities of safety fibers used by the industries which use them.
  • This dyeing process which allows dyeing fibers with rare earth chelates is carried out in two different ways.
  • the method basically consists in using as a dyeing medium a bath containing a combination of one or more solvents in which the rare earth chelates used are soluble, and one or more diluents in which the chelates Rare Earths are insoluble or poorly soluble, and to be taken from the dye bath, all or part of the solvent in liquid or vapor phase.
  • This dyeing process already known in the prior art, has been used to dye with acid dyes and metalliferous acids, and those skilled in the art can find all the details in the literature, and in particular in french patents 2,054,430, 2,061,574, 2,088,081, 2,124,193.
  • Example 1 Numerous exemplary embodiments of dyeing safety fibers with luminescent rare earth chelates according to this first embodiment of the invention were produced by replacing, in examples 1 to 7 of French patent 2,054,430 and 1 to 9 of French patent 2,124,193 textile materials used by fibers, dyes used by luminescent chelates from Rare Earths; the proportions of chelates used to replace the dyes are of the same order of magnitude and are fixed as a function of the intensity of the fluorescent emission desired in the safety fibers.
  • the applicant has also found that a good dyeing of safety fibers is obtained by using a dyeing bath comprising only a solvent in which the chelates are soluble.
  • this process basically consists in forming and synthesizing Rare Earth chelate in the dye bath which contains the fibers to be dyed, and therefore in fibers to be dyed.
  • Example 2 1 kg of Fibranne fibers of 27 Dtex and 5 mm in length is introduced into a bath at 85 ° C formed of a aqueous solution / 20 Liters of 4.4.4.Trifloro.1.Phenyl.1.3.Butane- Sodium for 30 minutes; an aqueous solution of Terbium chloride which then causes the synthesis of the corresponding chelate and its precipitation in the fibers is then added with stoichiometric amount.
  • the fibers removed from the dye bath and dried still have their original whitish appearance, but are fluorescent in green under UV rays due to the presence of the chelate precipitated in the fibers.
  • aqueous bath of this example can be replaced by a water-solvent or pure solvent bath and useful reference to the literature on the manufacture of rare earth chelates.
  • the respective amounts of chelating agents and rare earth salts are fixed according to the nature of the chelate to be synthesized and the luminescence intensity sought in the fibers.
  • the working conditions of the dyeing bath are those usually used in the dyeing of textile fibers, in particular with regard to the temperature and the pressure which are selected according to the nature of the fibers to be dyed.
  • the fibers which can be used according to the first or second embodiment of this invention can be natural, artificial or synthetic, and without departing from the scope of this invention, textile materials can be dyed according to one or the other of these two modes. of the same nature as fibers, as well as continuous threads, films, natural artificial or synthetic resins.
  • This dyeing process can also be applied to fibers of the first and second group, that is to say already colored fibers (their color, for example yellow, being visible in sunlight or artificial dye) which will present after their / according to this invention a very interesting feature of additional luminescent emission (in this example the yellow fibers will also have a green fluorescene under UV if they have been dyed with a Terbium chelate according to one of the two methods described).
  • the fibers produced according to Examples 1 and 2 of this invention were added in small quantities to the paper pulp; a paper machine transformed this paper pulp into paper and an excellent security paper was thus produced comprising authentication marks which are invisible except under certain lighting conditions (U.V., I.R., or X).
  • the originator has also found that the luminescence of these rare earth chelates is sensitive to pH, being maximum at neutral pH and gradually declining as soon as the environment of the chelate moves away from this neutral pH.
  • the applicant has thus constituted either a new means of authentication, or a secret code, or a marking, for example, of the date of manufacture.
  • This new means of authentication was produced by incorporating security fibers dyed according to the invention in a security paper manufactured at ? It is acidic, and therefore the luminescence of the fibers quickly disappears.
  • this paper was immersed in an alcoholic solution of the chelating agent which had been used to synthesize the chelate used to dye the fibers, and we were able to authenticate this paper by the reappearance of the luminescence of the safety fibers.
  • the decline in luminescence of the dyed fibers according to this invention being proportional to the residence time of the fibers in their acid or basic support, this decline can be used to constitute a time scale elapsed in relation to a support of neutral character possibly serving as a reference.
  • a security paper produced at acidic pH and containing fibers of the invention a security label was produced which has been stuck on products and whose luminescence decline indicates for example the expiration date, the end warranty, or other deadlines.
  • This marking which constitutes a secret code and a time coding, is applicable in particular to transport tickets with limited validity and in general to the production of documents or other materials having value only for a limited period.

Abstract

The invention relates to security fibers and other allied materials made luminescent by a dyeing process employing rare-earth compounds and their applications in fiduciary documents and other materials requiring authentication.

Description

. La présente invention concerne des fibres de sécurité, des fils de sécurité, des matières textiles, des films plastiques et de cellulose régénérée, des résines plastiques, luminescents, leurs procédés de réalisation et leurs applications dans des documenta fiduciaires et autres matières. Les fibres de sécurité sont des fibres qui sont incorporées dans les documents fiduciaires ou autres matières aux fins d'assurer une identification, une authentification, une protection contre la contrefaçon, l'imitation ou la falsification. Les fils de sécurité sont des fils continus ou des bandes de film, introduits dans les documents fiduciaires aux mèmes'fins que les fibres de sécurité.. The present invention relates to security fibers, security threads, textile materials, plastic films and regenerated cellulose, plastic resins, luminescent, their production methods and their applications in fiduciary documents and other materials. Security fibers are fibers that are incorporated into fiduciary documents or other matters for the purpose of ensuring identification, authentication, protection against counterfeiting, imitation or falsification. The security threads are continuous threads or strips of film, introduced in the fiduciary documents for the same purpose as the safety fibers.

L'expression "documents fiduciaires" désigne ici et dans ce qui suit des papiers tels que papiers pour billets de banque, chèques, actions, valeurs, timbres, documents officiels, cartes d'identité, passeports, livrets, billets,,tickets, bons, bulletins, livres comptables, ainsi que les cartes de crédit, de paiement, d'accès, multifonctions, et documents analogues présentant nécessairement un haut niveau de sécurité.The expression “fiduciary documents” designates here and in the following papers such as papers for banknotes, checks, stocks, securities, stamps, official documents, identity cards, passports, booklets, tickets, tickets, vouchers , newsletters, books of account, as well as credit, payment, access, multifunction, and similar cards necessarily offering a high level of security.

L'expression "autres matières" désigne ici des matières qui, en vue de lutter contre leur contrefaçon,imitation ou falsification requièrent un moyen d'indentification, d'authentification et de protection obtenu par l'incorporation de fibres de sécurité dans ou sur ces matières.The expression “other materials” designates here materials which, in order to fight against their counterfeiting, imitation or falsification require a means of identification, authentication and protection obtained by the incorporation of security fibers in or on these materials.

Les fibres de sécutité incorporées dans ces documents fiduciaires et autres matières sont généralement classables ainsi :

  • - fibres visibles en lumière solaire ou artificielle,
  • - fibres visibles en lumière solaire ou artificielle et présentant une fluorescence sous les rayons ultra-violets,
  • - fibres invisibles en lumière solaire ou artificielle mais présentant une fluorescence sous les rayons ultra-violets. L'expression "fibres invisibles en lumière solaire ou artificielle" signifie que ces fibres qui sont fluorescentes sous les rayons infra-rouges, ultra-violets ou X , ont, à la lumière solaire ou artificielle, une couleur identique à celle qui était la leur avant le traitement qu'elles ont subi et qui les a rendu fluorescentes. Dans le cas le plus général de la fabrication d'un papier de sécurité blanc avant son impression, des fibres de sécurité blanchâtres sont incorporées à la pâte à papier blanche et ces fibres sont donc invisibles ou indscernables en ayant la même couleur que le papier; cependant, sous excitation par exemple de rayons ultra-violets, ces fibres émettent une fluorescence par exemple dans le bleu.
The security fibers incorporated in these fiduciary documents and other matters can generally be classified as follows:
  • - fibers visible in sunlight or artificial light,
  • - fibers visible in sunlight or artificial light and present both fluorescence under ultraviolet rays,
  • - fibers invisible in sunlight or artificial light but exhibiting fluorescence under ultraviolet rays. The expression "fibers invisible in sunlight or artificial light" means that these fibers which are fluorescent under infra-red, ultraviolet or X rays, have, in sunlight or artificial light, a color identical to that which was theirs before the treatment they underwent and which made them fluorescent. In the most general case of manufacturing a white security paper before printing, whitish security fibers are incorporated into the white paper pulp and these fibers are therefore invisible or indistinguishable by having the same color as the paper; however, under excitation, for example of ultraviolet rays, these fibers emit fluorescence, for example in blue.

La présente invention concerne la réalisation de fibres de préférence du dernier groupe qui sont donc invisibles en lumière solaire ou artificielle et qui sous excitation de rayons I.R., U.V., ou X, présentent une luminescence dans une ou plusieurs parties du spectre I.R.,' visible, U.V., ou X.The present invention relates to the production of fibers preferably from the last group which are therefore invisible in sunlight or artificial light and which, under excitation of IR, UV or X rays, exhibit luminescence in one or more parts of the visible IR spectrum . UV, or X.

Les colorants utilisés dans le cadre de cette invention sont des composés de Terres Rares, ou Lanthanides, de numéro atomique 57 à 71 auquels on rattache habituellement l'Yttrium et le Thorium de numéro atomique respectifs 39 et 90r Les composés de Terres Rares qui présentent ces caractéristiques de luminescence et utlisés dans c ette invention sont des Chélates.The dyes used in the context of this invention are Rare Earth compounds, or Lanthanides, with atomic number 57 to 71 to which are usually attached Yttrium and Thorium with atomic number 39 and 90 r Rare Earth compounds which have these luminescence characteristics and used in this invention are chelates.

Dans l'état de la technique antérieure, on a vu l'utilisation de très nombreux composés luminescents de Lanthanides aux fins d'identification notamment dans les documents fiduciaires, avec les brevets français 1 471 367 1 520 520, 2-289 976, 2 423 522, les demandes de brevets français 2 483 334, 2 484 920, 2484921, 2 484 922.In the state of the prior art, we have seen the use of numerous luminescent lanthanide compounds for identification purposes, in particular in fiduciary documents, with French patents 1,471,367. 1,520,520, 2-289,976, 2,423,522, French patent applications 2,483,334, 2,484,920, 2,484,921, 2,484,922.

Ces brevets et demandes de brevets, lorsqu'ils envisagent l'utilisation de chélates de Terres Rares, décrivent l'incorporation de ces chélates à des encres ou vernis par dissolution, ou par incorporation à la masse du papier.These patents and patent applications, when they envisage the use of rare earth chelates, describe the incorporation of these chelates into inks or varnishes by dissolution, or by incorporation into the mass of paper.

Lorsque ces brevets et demandes de brevets envisagent l'utilisation des chélates de Terres Rares dans; des fibres de sécurité, ces brevets et demandes de brevets n'en énoncent que l'idée mais sans en donner le mode de réalisation. On trouve par exemple dans les demandes de brevets français 2 484 922 et 2 484 334 que"la substance luminescente est représentée dans le papier par des fibres de sécurité préparées en conséquence pendant la fabrication du papier ". Or on sait d'une part que la préparation de fibres de sécurité n'est pas faite pendant la fabrication du papier, sauf à faire une teinture de la masse de papier et non de fibres de sécurité, et d'autre part que la préparation de véritables fibres de sécurité est une opération différente et antérieure chronologiquement à la fabrication du papier,; cette opération est faite par les industries de la teinture.When these patents and patent applications envisage the use of rare earth chelates in; security fibers, these patents and patent applications state only the idea but without giving the embodiment thereof. It is found, for example, in French patent applications 2,484,922 and 2,484,334 that "the luminescent substance is represented in the paper by security fibers prepared accordingly during the manufacture of the paper". Now it is known on the one hand that the preparation of security fibers is not made during the manufacture of paper, except for dyeing the mass of paper and not of security fibers, and on the other hand that the preparation real security fibers is a different operation and chronologically prior to papermaking; this operation is carried out by the dyeing industries.

L'homme de l'art, en l'occurrence, l'expert en teinture de fibres, ne peut pas, sur le seul énoncé de l'idée, effectuer une teinture de fibres avec ces luminophores de Terres Rares. En effet le procédé de teinture avec ces chélates n'est pas décrit car la réalisation de l'idée se heurte à une difficulté majeure : ces chélates, introduits dans un bain de teinture de fibres, sont insolubles dans l'eau et ne peuvent donc pénétrer dans les fibres par les procédés habituels de teinture de fibres.Those skilled in the art, in this case, the fiber dyeing expert, cannot, on the sole statement of the idea, carry out a fiber dyeing with these rare earth phosphors. Indeed, the dyeing process with these chelates is not described because the realization of the idea comes up against a major difficulty: these chelates, introduced into a fiber dye bath, are insoluble in water and therefore cannot penetrate the fibers by the usual fiber dyeing processes.

Pour résoudre cette difficulté, il a été proposé, notamment dans la demande de brevet allamand 31 224 70, d'ajouter ces chélates à la masse de filage utilisée pour extruder des fils continus ultérieurement coupés en fibres.To resolve this difficulty, it has been proposed, in particular in allamand patent application 31 224 70, to add these chelates to the spinning mass used to extrude continuous threads subsequently cut into fibers.

Ce mode de réalisation de fibres de sécurité, satisfaisant sur le plan théorique, présente dans la pratique de lourdes contraintes : en effet les fabricants-extrudeurs de fils continus, qui pourraient incorporer à leur masse de filage des chélates de Terres Rares ne souhaitent pas modifier la composition de leur masse de filage pour de petites fabrications, alors que les fibres de sécurité, obtenues à partir de ces fils continus coupés, ne représenteraient vu leurs utilisations et leur prix qu'une infime proportion de la production mensuelle ou même journalière de ces fabricants-extrudeurs de fils continus.This embodiment of safety fibers, satisfactory on the theoretical level, presents in practice heavy constraints: in fact the manufacturers-extruders of continuous threads, which could incorporate into their spinning mass rare earth chelates do not wish to modify the composition of their spinning mass for small productions, while the safety fibers, obtained from these cut continuous yarns, given their uses and their prices, represent only a tiny proportion of the monthly or even daily production of these manufacturers and extruders of continuous yarns.

La présente invention propose donc de résoudre ces difficultés en décrivant un procédé de réalisation de fibres de sécurité dans lequel l'incorporation de chélates de lanthanides, d'Yttrium et de Thorium est faite non pas dans la masse de filage des fils continus, mais par un procédé de teinture de fibres déjà extrudées et coupées en fibres .The present invention therefore proposes to resolve these difficulties by describing a process for producing safety fibers in which the incorporation of lanthanide, Yttrium and Thorium chelates is done not in the spinning mass of continuous threads, but by a process for dyeing fibers already extruded and cut into fibers.

S'agissant d'un procédé de teinture, cette invention présente l'avantage d'avoir une certaine similitude avec les procédés de teinture utilisés par les teinturiers de fibres et donc d'utiliser des appareils presque standards à cette industrie, et d'offrir la possibilité de procéder à des cycles de fabrication compatibles avec les faibles quantités de fibres de sécurité utilisées par les industries qui en sont utilisatrices.Being a dyeing process, this invention has the advantage of having a certain similarity with the dyeing processes used by fiber dyers and therefore of using almost standard apparatuses in this industry, and of offering the possibility of carrying out manufacturing cycles compatible with the low quantities of safety fibers used by the industries which use them.

Ce procédé de teinture qui permet de teindre des fibres avec des chélates de Terres Rares est réalisé de deux façons differentes.This dyeing process which allows dyeing fibers with rare earth chelates is carried out in two different ways.

Dans le premier mode de réalisation, le procédé consiste fondamentalement à utiliser comme milieu de teinture un bain renfermant une combinaison d'un ou plusieurs solvants dans lesquels les chélates utilisés de Terres Rares sont solubles, et un ou des diluants dans lesquels les chélates de Terres Rares sont insolubles ou peu solubles, et à prélever du bain de teinture, tout ou partie du solvant en phase liquide ou vapeur. Ce procédé de teinture, déjà connu dans l'art antérieur de la technique, a été utilisé pour teindre avec des colorants acides et acides métallifères, et l'homme de l'art peut en trouver tous les détails dans la littérature, et notamment dans les brevets français 2 054 430, 2 061 574, 2 088 081, 2 124 193.In the first embodiment, the method basically consists in using as a dyeing medium a bath containing a combination of one or more solvents in which the rare earth chelates used are soluble, and one or more diluents in which the chelates Rare Earths are insoluble or poorly soluble, and to be taken from the dye bath, all or part of the solvent in liquid or vapor phase. This dyeing process, already known in the prior art, has been used to dye with acid dyes and metalliferous acids, and those skilled in the art can find all the details in the literature, and in particular in french patents 2,054,430, 2,061,574, 2,088,081, 2,124,193.

Exemple 1 : De nombreux exemples de réalisation de teinture de fibres de sécurité avec des chélates de Terres Rares luminescents selon ce premier mode de réalisation de l'invention ont été réalisés en remplaçant,dans les exemples 1 à 7 du brevet français 2 054 430 et 1 à 9 du brevet français 2 124 193 les matériaux textiles utilisés par des fibres, les colorants utilisés par des chélates luminescents de Terres Rares ; les proportions de chélates utilisés en remplacement des colorants sont du même ordre de grandeur et sont fixés en fonction de l'intensité de l'émission fluorescente recherchée dans les fibres de sécurité.Example 1: Numerous exemplary embodiments of dyeing safety fibers with luminescent rare earth chelates according to this first embodiment of the invention were produced by replacing, in examples 1 to 7 of French patent 2,054,430 and 1 to 9 of French patent 2,124,193 textile materials used by fibers, dyes used by luminescent chelates from Rare Earths; the proportions of chelates used to replace the dyes are of the same order of magnitude and are fixed as a function of the intensity of the fluorescent emission desired in the safety fibers.

Le demandeur a également trouvé qu'on obtient une bonne teinture de fibres de sécurité en utilisant un bain de teinture comportant uniquement un solvant dans lequel les chélates sont solubles.The applicant has also found that a good dyeing of safety fibers is obtained by using a dyeing bath comprising only a solvent in which the chelates are soluble.

Dans le deuxième mode de réalisation de teinture de fibres de sécurité avec des chélates de Terres Rares, ce procédé consiste fondamentalement à former et à faire la synthèse du chélate de Terres Rares dans le bain de teinture qui contient les fibres à teindre, et donc dans les fibres à teindre.In the second embodiment of dyeing safety fibers with Rare Earth chelates, this process basically consists in forming and synthesizing Rare Earth chelate in the dye bath which contains the fibers to be dyed, and therefore in fibers to be dyed.

L'exemple unique qui suit illustre à titre non limitatif ce deuxième de réalisation de l'invention. Exemple 2 ; 1 Kg de fibres de Fibranne de 27 Dtex et 5 MM de longueur est introduit dans un bain à 85°C formé d'une aqueuse solution/de 20 Litres de 4.4.4.Trifloro.1.Phenyl.1.3.Butane- dione de Sodium pendant 30 minutes; on ajoute alors sous agitation en quantité stoéchiométrique une solution aqueuse de chlorure de Terbium qui provoque la synthèse du chélate correspondant et sa précipitation dans les fibres. Les fibres sorties du bain de teinture et séchées, ont toujours leur aspect blanchâtre originel, mais sont fluorescentes dans le vert sous les rayons U.V. par suite de la présence du chélate précipité dans les fibres.The following unique example illustrates, without limitation, this second embodiment of the invention. Example 2; 1 kg of Fibranne fibers of 27 Dtex and 5 mm in length is introduced into a bath at 85 ° C formed of a aqueous solution / 20 Liters of 4.4.4.Trifloro.1.Phenyl.1.3.Butane- Sodium for 30 minutes; an aqueous solution of Terbium chloride which then causes the synthesis of the corresponding chelate and its precipitation in the fibers is then added with stoichiometric amount. The fibers removed from the dye bath and dried, still have their original whitish appearance, but are fluorescent in green under UV rays due to the presence of the chelate precipitated in the fibers.

On peut remplacer le bain aqueux de cet exemple par un bain eau-solvant ou solvant pure et se référer utilement à la littérature sur la fabrication des chélates de Terres Rares.The aqueous bath of this example can be replaced by a water-solvent or pure solvent bath and useful reference to the literature on the manufacture of rare earth chelates.

Les quantités respectives des agents chélatants et des sels de Terres Rares sont fixées en fonction de la nature du chélate à synthétiser et de l'intensité de luminescence recherchée dans les fibres.The respective amounts of chelating agents and rare earth salts are fixed according to the nature of the chelate to be synthesized and the luminescence intensity sought in the fibers.

Les conditions de travail du'bain de teinture sont celles habituellement utiiisées dans la teinture de fibres textiles, notamment en ce qui concerne la température et la pression qui sont sélectionnées en fonction de la nature des fibres à teindre.The working conditions of the dyeing bath are those usually used in the dyeing of textile fibers, in particular with regard to the temperature and the pressure which are selected according to the nature of the fibers to be dyed.

Les fibres utilisables selon le premier ou le deuxième mode de réalisation de cette invention peuvent être naturelles, artificielles ou synthétiques, et sans sortir du cadre de cette invention, on peut teindre selon l(un ou l'autre de ces deux modes des matériaux textiles de même nature que les fibres, ainsi que des fils continus, des films, des résines naturelles artificielles ou synthétiques.The fibers which can be used according to the first or second embodiment of this invention can be natural, artificial or synthetic, and without departing from the scope of this invention, textile materials can be dyed according to one or the other of these two modes. of the same nature as fibers, as well as continuous threads, films, natural artificial or synthetic resins.

Ce procédé de teinture peut également être appliqué à des fibres du premier et du deuxième groupe, c'est à dire à des fibres déjà colorées ( leur couleur,par exemple jaune, étant visible à la lumière solaire ou teinture artificielle ) qui présenteront après leur/selon cette invention une caractéristique très intéressante d'émission luminescente supplémentaire ( dans cet exemple les fibres jaunes auront également une fluorescene verte sous les U.V. si elles ont-été teintes avec un chélate de Terbium selon l'un des deux procédés décrits).This dyeing process can also be applied to fibers of the first and second group, that is to say already colored fibers (their color, for example yellow, being visible in sunlight or artificial dye) which will present after their / according to this invention a very interesting feature of additional luminescent emission (in this example the yellow fibers will also have a green fluorescene under UV if they have been dyed with a Terbium chelate according to one of the two methods described).

Les fibres réalisées selon les exemples 1 et 2 de cette invention ont été ajoutées en faible quantité à la pâte à papier; une machine à papier a transformé cette pâte à papier en papier et on a réalisé ainsi un excellent papier de sécurité comportant des marques d'authentification qui sont invisibles sauf dans certaines conditions d'éclairage (U.V., I.R., ou X).The fibers produced according to Examples 1 and 2 of this invention were added in small quantities to the paper pulp; a paper machine transformed this paper pulp into paper and an excellent security paper was thus produced comprising authentication marks which are invisible except under certain lighting conditions (U.V., I.R., or X).

Le emandeur a également trouvé que la luminescence de ces chélates de Terres Rares est sensible aupH, en étant maximale à pH neutre et en déclinant progressivement des que l'environnement du chélate s'éloigne de ce pH neutre.The originator has also found that the luminescence of these rare earth chelates is sensitive to pH, being maximum at neutral pH and gradually declining as soon as the environment of the chelate moves away from this neutral pH.

En effectuant un controle précis de ce déclin de luminescence, le demandeur a ainsi constitué soit un nouveau moyen d'authentification, soit un code secret, soit un marquage par exemple de la date de fabrication.By carrying out a precise control of this decline in luminescence, the applicant has thus constituted either a new means of authentication, or a secret code, or a marking, for example, of the date of manufacture.

Ce nouveau moyen d'authentification a été réalisé en incorporant des fibres de sécurité teintes selon l'invention dans un papier de sécurité fabriqué à ?H acide, et de ce fait la luminescence des fibres a rapidement disparue. Lors du test d'authentification de ce papier de sécurité, on a immergé ce papier dans une solution alcoolique de l'agent chélatant qui avait été utilisé pou faire la synthèse du chélate employé pour teindre les fibres, et on a pu authentifier ce papier par la réapparition de la luminescence des fibres de sécurité.This new means of authentication was produced by incorporating security fibers dyed according to the invention in a security paper manufactured at ? It is acidic, and therefore the luminescence of the fibers quickly disappears. During the authentication test of this security paper, this paper was immersed in an alcoholic solution of the chelating agent which had been used to synthesize the chelate used to dye the fibers, and we were able to authenticate this paper by the reappearance of the luminescence of the safety fibers.

Inversement, on a pu faire un autre test d'authentification d'un papier de sécurité fabriqué à pH 7 et comportant des fibres luminescentes selon l'invention, en l'immergeant dans une solution acide et en constatant le déclin de la luminescence des fibres de sécurité, ce qui a permis une authentification intéressante.Conversely, another authentication test of a security paper made at pH 7 and comprising luminescent fibers according to the invention could be made, by immersing it in an acid solution and noting the decline. of the luminescence of the security fibers, which enabled an interesting authentication.

Le déclin de luminescence des fibres teintes selon cette invention étant proportionnel au temps de séjour des fibres dans leur support acide ou basique, ce déclin peut être utilisé pour constituer une échelle de temps écoulé par rapport à un support à caractère neutre servant éventuellement de référence. A partir d'un papier de sécurité fabriqué à pH acide et contenant des fibres de l'invention, on a réalisé une étiquette de sécurité qui a été collétsur des produits et dont le déclin de luminescence indique par exemple la date de peremption, la fin de la garantie, ou autres dates limites. Ce marquage qui constitue un code secret et un codage du temps, est aplicable notamment aux titres de transport à validité limitée et d'une façon générale à la réalisation de documents ou autres matières n'ayant de valeur que pendant une durée limitée.The decline in luminescence of the dyed fibers according to this invention being proportional to the residence time of the fibers in their acid or basic support, this decline can be used to constitute a time scale elapsed in relation to a support of neutral character possibly serving as a reference. From a security paper produced at acidic pH and containing fibers of the invention, a security label was produced which has been stuck on products and whose luminescence decline indicates for example the expiration date, the end warranty, or other deadlines. This marking, which constitutes a secret code and a time coding, is applicable in particular to transport tickets with limited validity and in general to the production of documents or other materials having value only for a limited period.

Claims (10)

1- Procédé de réalisation de fibres de sécurité, fils de sécurité, matières textiles, films plastiques ou de cellulose régénérée, résines naturelles, artificielles. ou synthétiques, luminescents caractérisé par le fait que l'introduction de chélates luminescents de Terres Rares, dans ces matières, est faite, à un stade postérieur à leur fabrication dans laquelle ces chélates n'ont pas été employés, par un procédé de teinture de ces matières avec ces chélates.1- Process for making safety fibers, safety threads, textiles, plastic films or regenerated cellulose, natural and artificial resins. or synthetic, luminescent, characterized in that the introduction of rare earth luminescent chelates into these materials is made, at a stage subsequent to their manufacture in which these chelates have not been used, by a dyeing process of these materials with these chelates. 2- Procédé de réalisation de fibres de sécurité selon la revendication 1 caractérisé par le fait que ces matières sont rendues luminescentes par un procédé de teinture comportant dans un bain de teinture au moins un chélate luminescent de Terres Rares dissous dans au moins un solvant, et au moins un diluant dans lequel le chélate est insoluble ou peu soluble, et consistant à prélever en fin de teinture tout ou partie du solvant en phase liquide ou vapeur.2- A process for producing safety fibers according to claim 1, characterized in that these materials are made luminescent by a dyeing process comprising in a dyeing bath at least one luminescent chelate of Rare Earths dissolved in at least one solvent, and at least one diluent in which the chelate is insoluble or sparingly soluble, and consisting in taking at the end of dyeing all or part of the solvent in liquid or vapor phase. 3- Procédé de réalisation de fibres de sécurité selon la revendication 1 caractérisé par le fait que ces matières sont rendues luminescentes par un procédé de teinture comportant dans le bain de teinture seulement un ou des solvants dans lequel ou lesquels ces chélates sont dissous.3- A method of producing safety fibers according to claim 1 characterized in that these materials are made luminescent by a dyeing process comprising in the dyeing bath only one or more solvents in which or which these chelates are dissolved. 4- Procédé de réalisation de fibres de sécurité selon la revendication 1 caractérisé par le fait que ces matières sont rendues luminescentes par un procédé de teinture au cours duquel la synthèse du chélate est effectué et qui entraine sa précipitation dans les matières geindre.4- A method of producing safety fibers according to claim 1 characterized in that these materials are made luminescent by a dyeing process during which the synthesis of the chelate is carried out and which causes its precipitation in the whining materials. 5- Procédé de réalisation de fibres de sécurité selon l'une quelconque des revendications 1 à 4 caractérisé par le fait que ce procédé de teinture confère à ces matières ainsi teintes la propriéré d'émettre au moins une luminescence dans uns partie quelconque du spectre infra-rouge, visible, ultra-violet ou X, sous excitation de rayons infra-rouges, ultra-violets ou X.5- A method of producing security fibers according to any one of claims 1 to 4 characterized by the fact that this dyeing process gives these dyed materials the property of emitting at least one luminescence in any part of the infrared, visible, ultra-violet or X spectrum, under excitation of infrared rays, ultraviolet or X. 6- Procédé de réalisation de fibres de sécurité selon l'une quelconque des revendications 1 à 4 caractérisé par le fait que ce procédé de teinture ne modifie pas la couleur, visible en lumière solaire ou artificielle, de ces matières.6- A process for producing safety fibers according to any one of claims 1 to 4 characterized in that this dyeing process does not modify the color, visible in sunlight or artificial light, of these materials. 7- Fibres de sécurité réalisées selon l'une quelconque des revendications 1 à 4 caractérisées par le fait que ces matières ont après leur teinture la même couleur en lumière solaire ou artificielle qu'avant leur teinture.7- security fibers made according to any one of claims 1 to 4 characterized in that these materials have after their dyeing the same color in sunlight or artificial light as before their dyeing. 8- Fibres de sécurité réalisées selon l'une quelconque des revndications 1 à 4 caractérisées par le fait qu' elles présentent au moins une émission de luminescence dans une partie du spectre infra-rouge, visible, ultra-violet ou X, sous excitation de rayons infra-rouges, ultra-violets ou X.8- Safety fibers produced according to any one of claims 1 to 4, characterized in that they exhibit at least one luminescence emission in part of the infrared spectrum, visible, ultra-violet or X, under excitation of infrared, ultraviolet or X rays. 9- Documents fiduciaires et autres matières requérant un moyen d'authentification caractérisés par comportent le fait qu'ils, dans la masse ou en surface, des fibres de sécurité réalisées selon l'une quelconque des revendications 1 à 4 et présentant des propriétés conformes aux revendications 7 à 8.9- Fiduciary documents and other matters requiring a means of authentication characterized by include the fact that, in the mass or on the surface, security fibers produced according to any one of claims 1 to 4 and having properties in accordance with claims 7 to 8. 10- Documents fiduciaires et autres matières requérant un moyen d'authentification, réalisés selon la revendication 9, caractérisés par le fait que la modification cbntrollée et volontaire de leur luminescence par une action sur leur pH de fabrication ou d'utilisation constitue une échelle de temps incorporée, une marque d'authentification ou un code secret.10- Fiduciary documents and other materials requiring a means of authentication, produced according to claim 9, characterized in that the controlled and voluntary modification of their luminescence by an action on their manufacturing or use pH constitutes a time scale incorporated, an authentication mark or a secret code.
EP85401148A 1984-06-22 1985-06-11 Process for the production of luminescent security fibres and other related materials Expired - Lifetime EP0169750B2 (en)

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AT85401148T ATE37053T1 (en) 1984-06-22 1985-06-11 FLASHING SECURITY FIBERS; SECURITY PAPER AND OTHER MATERIALS CONTAINING THESE FIBERS.

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FR8409807A FR2566440B1 (en) 1984-06-22 1984-06-22 SECURITY FIBERS AND OTHER MATERIALS MADE LUMINESCENT BY A DYEING PROCESS, THEIR PROCESSES AND THEIR APPLICATIONS

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EP0169750B1 (en) 1988-09-07
US4655788A (en) 1987-04-07
FR2566440A1 (en) 1985-12-27
FR2566440B1 (en) 1988-07-22
ATE37053T1 (en) 1988-09-15
US4921280A (en) 1990-05-01
EP0169750B2 (en) 1997-01-15
DE3564832D1 (en) 1988-10-13

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