EP0271941B1 - Method for manufacturing a transfer product with a protection layer, and product obtained for the protection of documents or other produce - Google Patents

Method for manufacturing a transfer product with a protection layer, and product obtained for the protection of documents or other produce Download PDF

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Publication number
EP0271941B1
EP0271941B1 EP87202288A EP87202288A EP0271941B1 EP 0271941 B1 EP0271941 B1 EP 0271941B1 EP 87202288 A EP87202288 A EP 87202288A EP 87202288 A EP87202288 A EP 87202288A EP 0271941 B1 EP0271941 B1 EP 0271941B1
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EP
European Patent Office
Prior art keywords
imprint
film
mixture
process according
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP87202288A
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German (de)
French (fr)
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EP0271941A1 (en
Inventor
Louis Vernhet
François Trantoul
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Individual
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Individual
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Priority to AT87202288T priority Critical patent/ATE56667T1/en
Publication of EP0271941A1 publication Critical patent/EP0271941A1/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/12—Transfer pictures or the like, e.g. decalcomanias
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0027—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or layers by lamination or by fusion of the coatings or layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/162—Decalcomanias with a transfer layer comprising indicia with definite outlines such as letters and with means facilitating the desired fitting to the permanent base
    • 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
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/916—Fraud or tamper detecting
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24851—Intermediate layer is discontinuous or differential
    • Y10T428/24868—Translucent outer layer
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24851—Intermediate layer is discontinuous or differential
    • Y10T428/24868—Translucent outer layer
    • Y10T428/24876—Intermediate layer contains particulate material [e.g., pigment, etc.]

Definitions

  • the invention relates to a method for producing a protective product with a transferable protective film, which can be used to cover and protect a document or other element on the surface. It extends to the protection product obtained.
  • cellulosic or nitrocellulose transfer films are known in the field of decalcomania (see for example patent FR-A 2 427 208) or films obtained by alkyd-urethane deposition (see for example patent US-A 4,308,310), which are used to decorate a surface with a pattern.
  • these marking films cannot be used to meet the protection objectives targeted by the invention, because they are very fragile and do not resist light solvents and, a fortiori, more powerful solvents such as cellulose diluents; in particular, these films can be easily removed without altering the support and therefore cannot constitute protection against falsification.
  • the patent FR-A 2 391 859 describes labeling products which are heat transferable and comprise a thermoplastic polyurethane elastomer.
  • the transfer temperature must be sufficient to modify the structure of the polyurethane so as to generate covalent bonds ensuring adhesion to the support: this temperature inevitably generates cross-linking and hardening at the heart of the material, which would modify the flexibility characteristics of the document. if these products were used as a protective film.
  • the present invention proposes to provide a new protection product which can be used cold by simple pressure, in the manner of a transfer film by any person without any particular material.
  • the essential objective of the invention is to provide a product which gives very reliable protection both with regard to external stressors and against forgery; in particular, the invention aims to provide a product having a transferable protective film which is resistant to light solvents as well as to cellulosic solvents and whose elimination or attempted elimination is necessarily accompanied by destruction or very apparent alteration of the document, for most of the constituent materials and in particular for paper documents.
  • Another objective is to make it possible to personalize the document, by adding to it patterns or a screen, either directly visible, or invisible in sunlight but detectable under ultraviolet radiation.
  • Another objective is to avoid significantly modifying the physical characteristics of the protected document and in particular to preserve it with flexibility and folding possibilities similar to those which it initially possessed.
  • Another objective of the invention is to indicate a process for producing the targeted protection product benefiting from a low cost price, this cost, combined with the ease of implementation of the product, making it possible to generalize the use of the produced to the most common documents.
  • Another objective is to indicate a process suitable for obtaining transferable protective films, of various shapes depending on the envisaged end use.
  • the process referred to by the invention for producing a protective product with a protective film which can be cold transferred by simple pressure, uses as a base a layer obtained by printing using a two-component polymerizable liquid mixture containing a hydroxylated polyol and an isocyanate or polyisocyanate, a mixture capable of polymerizing in situ to result in a thin transparent layer of polyurethane.
  • the process according to the invention for the manufacture of the protective product consists in producing a single impression on a non-stick support sheet by means of a polymerizable liquid mixture as shown below. above defined so as to obtain, after in situ polymerization, a thin transparent film of polyurethane on said support sheet, and to cover said film with a transparent adhesive layer.
  • the method of the invention leads to coating by printing the support sheet with a thin polyurethane film, monolayer in the first case, multilayer in the second.
  • Each printing can be carried out by any printing process known per se and in particular by screen printing or rotogravure.
  • the liquid mixture used for printing is prepared beforehand in particular in a proportion of 1.8 to 2.2 doses of hydroxylated polyol for a dose of isocyanate or polyisocyanate.
  • the adhesive layer covering this film can in turn be produced, before complete polymerization of the last layer of the film, by printing the latter by means of transparent adhesive material, in particular by serigraphy or rotogravure.
  • the adhesive material used is for example of the acrylic type known per se.
  • a silicone protective sheet (or similarly treated) is then placed over the adhesive layer to protect it until use.
  • a protective product is thus obtained which is in sheet form, which can be distributed to the end user and whose implementation by the latter is extremely simple and requires no equipment.
  • Such a process, carried out cold without any particular precautions, can be carried out by any person without any particular skill.
  • the intermediate layer located in an inaccessible position between the other two allows the documents to be protected to be tamper-proof.
  • the colored substance placed in the polymerizable mixture of this intermediate layer will depend on the applications: invisible substance reacting to ultraviolet (or possibly infrared), visible substance undergoing a color change under radiation (ultraviolet %), opaque substance forming a pattern or an opaque frame on the document or parts of it.
  • the protective film according to the invention can be easily adapted to cover and protect one or more surfaces of determined shapes; it suffices that the impression (s) by means of the polymerizable liquid mixture (s), then the impression by means of the adhesive material are carried out on one or portions of the support sheet of shapes corresponding to those of the surfaces to be protected. It should be noted that the process of the invention makes it possible to produce protective products suitable for covering large areas, at a reduced cost, taking into account the extreme thinness of the polyurethane film and therefore the low quantities of materials. first used.
  • the method illustrated by way of example is implemented on screen printing machines, in particular on traditional snap-on machines (hinged screen) or on machines with integral lifting screen (screen movable in translation).
  • the two types of machine can be used interchangeably.
  • greater thicknesses between 10 and 50 ⁇ rn (microns)
  • the monolayer film product referred to in Figures (1 a-lc) comprises a transparent support sheet 1 ( Figure 1a) of the so-called non-adherent type, that is to say capable of developing only weak bonding forces with the most polymers.
  • this support sheet can be a polystyrene sheet with a grammage of the order of 120 g / m2.
  • This support sheet 1 is chosen to be larger than that of the surface to be protected.
  • This mixture can in particular be prepared by adding two doses of hydroxylated polyacrylic resin or hydroxylated polyester resin, or of low molecular weight hydroxylated polyether resin, and a dose of aliphatic or aromatic trifunctional polyisocyanate (for example, polyacrylic resin "ref. U8560” and trimerized hexamethylene diisocyanate “ref. U8580", sold by the "CHIMITEC Laboratory”).
  • hydroxylated polyacrylic resin or hydroxylated polyester resin or of low molecular weight hydroxylated polyether resin
  • aliphatic or aromatic trifunctional polyisocyanate for example, polyacrylic resin "ref. U8560” and trimerized hexamethylene diisocyanate "ref. U8580", sold by the "CHIMITEC Laboratory”
  • the quantity of mixture spread on the screen printing screen is adjusted to correspond to a thickness of 8 to 10 microns.
  • the mixture After printing on the support sheet 1, the mixture polymerizes and gives a thin transparent polyurethane film 2.
  • the printing is carried out in a shape corresponding to that of the surface to be protected, for example rectangular in the case shown diagrammatically in FIGS. 2a, 2b, 2c for the protection of identity cards.
  • the screen printing machine is cleaned every hour to prevent screen clogging.
  • the support sheet 1 and its polyurethane print 2 are then left in the open air in order to allow the polymerization to start.
  • the total duration of this is several days (of the order of 8 to 10 days).
  • the assembly is replaced on the screen printing machine to make a new impression above the film 2 by means of a transparent adhesive material.
  • the film will be allowed to polymerize between 3 and 36 hours and preferably approximately 4 or 5 hours. These periods make it possible to guarantee that the film is sufficiently dry and consistent to undergo printing but with a polymerization still incomplete to allow better adhesion of the new printing.
  • This will for example be carried out using an acrylic adhesive material of the type sold by "TIFLEX" under the reference "acrylic adhesive”.
  • This printing is carried out on the entire surface of the film 2 in order to coat it with a transparent adhesive layer 3 (FIG. 1b) whose thickness is similar to that of the film (between 5 and 50 microns and, in the example of 8 to 10 microns).
  • a silicone protective sheet 4 (FIG. 1c), the grammage of which can be of the order of 145 gr / m2.
  • the protection product thus obtained can be stored and distributed without special precautions.
  • FIGs 2a, 2b and 2c there is shown schematically an application of the invention for the protection of identity cards.
  • This protection may be carried out by the administration responsible for establishing these cards, after the holder has affixed his signature and, where appropriate, fingerprints, at the same time as the identity card is given to him.
  • the protection product is shown diagrammatically in perspective in FIG. 2a, the silicone protective sheet 4 being removed.
  • the product After removing this protective sheet, the product is applied to the identity card (FIG. 2b), the impressions 2 and 3 of polyurethane and adhesive material having the shape of a rectangle of size corresponding to that of this card. These prints are matched to the surface of the card and the operator applies pressure which causes the adhesive layer 3 to adhere to the card with simultaneous transfer of the film 2.
  • the protective film is not very visible and does not significantly modify the flexibility of the card.
  • FIGS. 3a-3e illustrate (on a larger scale) the manufacture of a protection product with a multilayer polyurethane film.
  • the first step (FIGS. 3a) is similar to the first step of the process already described and consists in printing on a polystyrene support sheet 5 a transparent layer of polyurethane 6 by means of a polymerizable mixture identical to that already described.
  • a discontinuous intermediate printing 7 of drawings, patterns or screens is carried out on the first printing (FIG. 3b ).
  • a delay of the order of 4 to 5 hours gives good results (initial printing sufficiently consistent to allow intermediate printing, while allowing close adhesion of the layers due to the simultaneous polymerization phenomena at their interface).
  • a second printing 8 is carried out identical to printing 6 in order to obtain a new transparent layer of polyurethane (FIG. 3c).
  • This printing is carried out in the same time as previously (between 3 and 36 hours and preferably 4 to 5 hours after the interlayer printing).
  • This multilayer film may in particular have a thickness of the order of 8 to 20 microns.
  • Printing of transparent adhesive material 9 is then carried out as previously (FIG. 3d). This impression is preferably made having complete polymerization of the layer 8 within a period of between 3 and 36 hours and preferably of the order of 4 to 5 hours.
  • the assembly is then covered by a silicone protective sheet 10 similar to that of the product previously described.
  • the protection product thus obtained can be stored and distributed without special precautions. Its use is similar to that already described for the product with a single-layer polyurethane film. It should be noted that, if necessary, several intermediate prints can be superimposed by successive passes on the machine (with a delay between passes of between 3 and 36 hours and preferably of the order of 4 to 5 hours).

Landscapes

  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Printing Methods (AREA)
  • Decoration By Transfer Pictures (AREA)
  • Cephalosporin Compounds (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Coils Or Transformers For Communication (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

1. Process for bringing about a protective product with a protective film capable of being transferred in the cold state by simple pressure, which can be used for covering end protecting on the surface a document or other object, characterised in that it consists in producing on a non-adhesive support foil (1) an imprint (2) by means of a liquid polymerisable two-component mixture containing a hydroxylated polyol and an isocyanate or polhisocyanate so as to cause polymerisation of the mixture in situ, leading to a thin transparent polyurethane film, and in covering said film with a transparent adhesive layer (3).

Description

L'invention concerne un procédé de réalisation d'un produit de protection à film protecteur transférable, utilisable pour couvrir et protéger en surface un document ou autre élément. Elle s'étend au produit de protection obtenu.The invention relates to a method for producing a protective product with a transferable protective film, which can be used to cover and protect a document or other element on the surface. It extends to the protection product obtained.

Il est souvent souhaitable de protéger des documents notamment en papier, soit pour les mettre à l'abri des facteurs d'agressions externes tels que l'humidité (cartes, plans utilisés à l'extérieur...), soit pour éviter qu'ils soient falsifiés et les rendre inviolables (papiers d'identité, documents administratifs...).It is often desirable to protect documents, in particular paper, either to protect them from external aggression factors such as humidity (maps, plans used outside ...), or to avoid that they are falsified and make them inviolable (identity papers, administrative documents ...).

Actuellement, une telle protection est obtenue par plastification à chaud (voir par exemple le brevet FR-A 1 549 724) ; un tel procédé impose un matériel professionnel et sa mise en oeuvre est resér- vée à des spécialistes. Ces conditions de mise en oeuvre et le coût de ce procédé en limitent les applications à des domaines spécifiques étroits (documents importants ou de valeur, petites surfaces à couvrir...) et excluent une généralisation à des documents courants. De plus, la plastification conduit à couvrir le document d'une couche relativement épaisse (à base de polyvinyle) et modifie les caractéristiques du document qui perd une grande partie de sa souplesse et n'est plus pliable ou manipulable comme auparavant.Currently, such protection is obtained by hot plasticization (see for example patent FR-A 1,549,724); such a process requires professional equipment and its implementation is reserved for specialists. These conditions of implementation and the cost of this process limit their applications to specific narrow areas (important or valuable documents, small areas to be covered ...) and exclude a generalization to current documents. In addition, the plasticization leads to covering the document with a relatively thick layer (based on polyvinyl) and modifies the characteristics of the document which loses a large part of its flexibility and is no longer foldable or easy to handle as before.

Par ailleurs, on connaît dans le domaine de la décalcomanie des films transferts cellulosiques ou ni- trocellulosiques (voir par exemple le brevet FR-A 2 427 208) ou des films obtenus par dépôt alkyde-uréthanne (voir par exemple le brevet US-A 4 308 310), qui sont utilisés pour garnir une surface d'un motif. Mais ces films de marquage sont inutilisables pour répondre aux objectifs de protection visés par l'invention, car ils sont très fragiles et ne résistent pas aux solvants légers et, a fortiori, à des solvants plus puissants tels que les diluants cellulosiques ; en particulier, ces films peuvent être facilement éliminés sans altérer le support et ne peuvent donc constituer une protection contre les falsifications.In addition, cellulosic or nitrocellulose transfer films are known in the field of decalcomania (see for example patent FR-A 2 427 208) or films obtained by alkyd-urethane deposition (see for example patent US-A 4,308,310), which are used to decorate a surface with a pattern. However, these marking films cannot be used to meet the protection objectives targeted by the invention, because they are very fragile and do not resist light solvents and, a fortiori, more powerful solvents such as cellulose diluents; in particular, these films can be easily removed without altering the support and therefore cannot constitute protection against falsification.

De plus, il est à noter que le brevet FR-A 2 391 859 décrit des produits de marquage qui sont transférables à chaud et comprennent un élastomère de polyurethane thermoplastique. La température de transfert doit être suffisante pour modifier la structure du polyuréthane de façon à engendrer des liaisons covalentes assurant l'adhésion sur le support: cette température engendre inévitablement au coeur du matériau des réticulations et un durcissement, qui modifieraient les caractéristiques de souplesse du document si ces produits étaient utilisés comme film de protection.In addition, it should be noted that the patent FR-A 2 391 859 describes labeling products which are heat transferable and comprise a thermoplastic polyurethane elastomer. The transfer temperature must be sufficient to modify the structure of the polyurethane so as to generate covalent bonds ensuring adhesion to the support: this temperature inevitably generates cross-linking and hardening at the heart of the material, which would modify the flexibility characteristics of the document. if these products were used as a protective film.

La présente invention se propose de fournir un nouveau produit de protection utilisable à froid par simple pression, à la manière d'un film transfert par toute personne sans aucun matériel particulier.The present invention proposes to provide a new protection product which can be used cold by simple pressure, in the manner of a transfer film by any person without any particular material.

L'objectif essentiel de l'invention est de fournir un produit qui donne une protection très sûre tant à l'égard des facteurs d'agression externes que vis- à-vis des falsifications; en particulier, l'invention vise à fournir un produit possédant un film protecteur transférable qui résiste aux solvants légers ainsi qu'aux solvants cellulosiques et dont l'élimination ou la tentative d'élimination s'accompagne nécessairement d'une destruction ou d'une altération très apparente du document, pour la plupart des matériaux constitutifs et notamment pour les documents en papier.The essential objective of the invention is to provide a product which gives very reliable protection both with regard to external stressors and against forgery; in particular, the invention aims to provide a product having a transferable protective film which is resistant to light solvents as well as to cellulosic solvents and whose elimination or attempted elimination is necessarily accompanied by destruction or very apparent alteration of the document, for most of the constituent materials and in particular for paper documents.

Un autre objectif est de permettre de personnaliser le document, en lui adjoignant des motifs ou une trame, soit directement visible, soit invisible à la lumière solaire mais détectable sous rayonnement ultraviolet.Another objective is to make it possible to personalize the document, by adding to it patterns or a screen, either directly visible, or invisible in sunlight but detectable under ultraviolet radiation.

Un autre objectif est d'éviter de modifier, de façon importante, les caractéristiques physiques du document protégé et de lui conserver en particulier une souplesse et des possibilités de pliage analogues à celles qu'il possédait initialement.Another objective is to avoid significantly modifying the physical characteristics of the protected document and in particular to preserve it with flexibility and folding possibilities similar to those which it initially possessed.

Un autre objectif de l'invention est d'indiquer un procédé de réalisation du produit de protection visé bénéficiant d'un faible coût de revient, ce coût, combiné à la facilité de mise en oeuvre du produit, permettant de généraliser l'utilisation du produit aux documents les plus courants.Another objective of the invention is to indicate a process for producing the targeted protection product benefiting from a low cost price, this cost, combined with the ease of implementation of the product, making it possible to generalize the use of the produced to the most common documents.

Un autre objectif est d'indiquer un procédé se prêtant à l'obtention de films protecteurs transférables, de formes diverses fonction de l'utilisation finale envisagée.Another objective is to indicate a process suitable for obtaining transferable protective films, of various shapes depending on the envisaged end use.

A cet effet, le procédé visé par l'invention, pour réaliser un produit de protection à film protecteur transférable à froid par simple pression, utilise comme base une couche obtenue par impression au moyen d'un mélange liquide bicomposant polymérisable contenant un polyol hydroxylé et un isocyanate ou polyisocyanate, mélange apte à polymériser in si- tu pour conduire à une mince couche transparente de polyuréthane.To this end, the process referred to by the invention, for producing a protective product with a protective film which can be cold transferred by simple pressure, uses as a base a layer obtained by printing using a two-component polymerizable liquid mixture containing a hydroxylated polyol and an isocyanate or polyisocyanate, a mixture capable of polymerizing in situ to result in a thin transparent layer of polyurethane.

Dans sa forme de mise en oeuvre la plus simple, le procédé conforme à l'invention pour la fabrication du produit de protection consiste à réaliser sur une feuille-support anti-adhérente une seule impression au moyen d'un mélange liquide polymérisable tel que ci-dessus défini de façon à obtenir après polymérisation in situ un mince film transparent de polyuréthane sur ladite feuille-support, et à couvrir ledit film d'une couche adhésive transparente.In its simplest form of implementation, the process according to the invention for the manufacture of the protective product consists in producing a single impression on a non-stick support sheet by means of a polymerizable liquid mixture as shown below. above defined so as to obtain, after in situ polymerization, a thin transparent film of polyurethane on said support sheet, and to cover said film with a transparent adhesive layer.

Dans une autre forme de mise en oeuvre adaptée pour fabriquer un produit de protection permettant de personnaliser un document ou autre élément, le procédé conforme à l'invention consiste :

  • . à réaliser sur une feuille-support anti-adhérente une première impression continue au moyen d'un mélange liquide polymérisable tel que défini plus haut, de façon à engendrer la polymérisation in situ du mélange conduisant à une première couche transparente de polyuréthane,
  • . avant polymérisation complète de cette première impression, à réaliser au moins une impression intercalaire selon un motif ou une trame au moyen d'un mélange liquide polymérisable tel que défini plus haut, avec adjonction d'une substance colorée parmi le groupe suivant : substance fluorescente sous radiation notamment ultraviolette, invisible à la lumière, substance fluorescente sous radiation notamment ultraviolette, visible à la lumière, ou pigment opaque, de façon à engendrer la polymérisation in situ dudit mélange conduisant à une couche intercalaire discontinue de polyuréthane,
  • . avant polymérisation complète de l'impression intercalaire, à réaliser une seconde impression continue au moyen d'un mélange liquide polymérisable tel que défini plus haut, de façon à engendrer la polymérisation in situ du mélange conduisant à une seconde couche transparente du polyuréthane,
  • . enfin à couvrir la seconde impression d'une couche adhésive transparente.
In another form of implementation suitable for manufacturing a protection product making it possible to personalize a document or other element, the method according to the invention consists:
  • . to carry out a first continuous impression on a non-stick support sheet by means of a polymerizable liquid mixture as defined above, so as to generate the in situ polymerization of the mixture leading to a first transparent layer of polyurethane,
  • . before complete polymerization of this first impression, to carry out at least one intermediate impression according to a pattern or a frame by means of a liquid polymerizable mixture as defined above, with the addition of a colored substance from the following group: fluorescent substance under radiation in particular ultraviolet, invisible to light, fluorescent substance under radiation in particular ultraviolet, visible in light, or opaque pigment, so as to generate the polymerization in situ tion of said mixture leading to a discontinuous interlayer of polyurethane,
  • . before complete polymerization of the intermediate printing, to carry out a second continuous printing by means of a liquid polymerizable mixture as defined above, so as to generate the in situ polymerization of the mixture leading to a second transparent layer of polyurethane,
  • . finally cover the second impression with a transparent adhesive layer.

Ainsi, le procédé de l'invention conduit à revêtir par impression la feuille-support d'un mince film de polyuréthane, monocouche dans le premier cas, multicouche dans le second. Chaque impression peut être réalisée par tout procédé d'impression connu en soi et en particulier par sérigraphie ou par héliogravure. Le mélange liquide servant à l'impression est préalablement préparé notamment à proportion de 1,8 à 2,2 doses de polyol hydroxylé pour une dose d'isocyanate ou de polyisocyanate. Par exemple, il est possible d'utiliser un mélange de résine polyacrylique hydroxylée ou de résine polyester hydroxylée ou de résine polyether hydroxylée, et de polyisocyanate aliphatique ou aromatique.Thus, the method of the invention leads to coating by printing the support sheet with a thin polyurethane film, monolayer in the first case, multilayer in the second. Each printing can be carried out by any printing process known per se and in particular by screen printing or rotogravure. The liquid mixture used for printing is prepared beforehand in particular in a proportion of 1.8 to 2.2 doses of hydroxylated polyol for a dose of isocyanate or polyisocyanate. For example, it is possible to use a mixture of hydroxylated polyacrylic resin or hydroxylated polyester resin or hydroxylated polyether resin, and aliphatic or aromatic polyisocyanate.

Cette technique permet d'obtenir des films de polyuréthane étanches, extrêmement minces et résistants, dont l'épaisseur pourra être ajustée en pratique entre 5 et 50 Ilm (microns). Dans le cas d'un film multicouche obtenu par plusieurs impressions, les diverses couches adhèrent intimement les unes aux autres en raison de leur polymérisation simultanée qui conduit à une interpénétration des molécules de polymère aux interfaces : le film obtenu est en réalité, non pas un complexe, mais un véritable composite où les couches en sont plus séparables. La couche intercalaire est ainsi rigoureusement inaccessible.This technique makes it possible to obtain waterproof, extremely thin and resistant polyurethane films, the thickness of which can be adjusted in practice between 5 and 50 μm (microns). In the case of a multilayer film obtained by several prints, the various layers adhere intimately to each other due to their simultaneous polymerization which leads to interpenetration of the polymer molecules at the interfaces: the film obtained is in reality, not a complex, but a real composite where the layers are more separable. The intermediate layer is thus strictly inaccessible.

La couche adhésive couvrant ce film peut à son tour être réalisée, avant polymérisation complète de la dernière couche du film, par impression de celle-ci au moyen de matière adhésive transparente, notamment par sérigraphie ou héliogravure. La matière adhésive utilisée est par exemple de type acrylique connu en soi.The adhesive layer covering this film can in turn be produced, before complete polymerization of the last layer of the film, by printing the latter by means of transparent adhesive material, in particular by serigraphy or rotogravure. The adhesive material used is for example of the acrylic type known per se.

Pour permettre une utilisation ultérieure du produit par l'usage, une feuille protectrice siliconée (ou traitée de façon analogue) est ensuite disposé au-dessus de la couche adhésive pour la protéger jusqu'à l'utilisation.To allow subsequent use of the product by use, a silicone protective sheet (or similarly treated) is then placed over the adhesive layer to protect it until use.

On obtient ainsi un produit de protection se présentant en feuille, qui peut être distribué auprès de l'utilisateur final et dont la mise en oeuvre par celui-ci est extrêmement simple et ne requiert aucun appareillage. Pour protéger un document ou toute surface analogue, il suffit de retirer la feuille siliconée, d'appliquer le produit à froid sur la surface à protéger de façon que la couche adhésive couvre cette surface, d'exercer une pression sur la surface de la feuille-support afin d'engendrer le transfert, et de détacher ladite feuille-support. Un tel processus mis en oeuvre à froid sans précautions particulières peut être accompli par toute personne sans compétence particulière.A protective product is thus obtained which is in sheet form, which can be distributed to the end user and whose implementation by the latter is extremely simple and requires no equipment. To protect a document or any similar surface, it is sufficient to remove the silicone sheet, to apply the product cold to the surface to be protected so that the adhesive layer covers this surface, to exert pressure on the surface of the sheet. -support in order to generate the transfer, and to detach said support sheet. Such a process, carried out cold without any particular precautions, can be carried out by any person without any particular skill.

Les essais ont démontré que l'on obtenait une protection extrêmement efficace des documents. Le film de polyuréthane, même très mince, soustrait les documents aux influences extérieures et est insensible à la plupart des solvants courants. Les rares solvants qui l'attaquent tels que l'acétone détruisent également le papier et les matériaux de ce type, de sorte que toute tentative d'altération du film pour accéder à la surface d'un document ainsi protégé laisse des traces très apparentes.Tests have shown that extremely effective document protection is achieved. Even very thin polyurethane film shields documents from external influences and is insensitive to most common solvents. The rare solvents that attack it, such as acetone, also destroy paper and similar materials, so that any attempt to alter the film to access the surface of a document thus protected leaves very visible traces.

En outre, dans le cas d'un film multicouche, la couche intercalaire située en position inaccessible entre les deux autres permet de personnaliser de façon infalsifiable les documents à protéger. La substance colorée disposée dans le mélange polymérisable de cette couche intercalaire dépendra des applications : substance invisible réagissant aux ultraviolets (ou éventuellement aux infrarouges), substance visible subissant une modification de couleur sous rayonnement (ultraviolets...), substance opaque formant un dessin ou une trame opaque sur le document ou des parties de celui-ci.In addition, in the case of a multilayer film, the intermediate layer located in an inaccessible position between the other two allows the documents to be protected to be tamper-proof. The colored substance placed in the polymerizable mixture of this intermediate layer will depend on the applications: invisible substance reacting to ultraviolet (or possibly infrared), visible substance undergoing a color change under radiation (ultraviolet ...), opaque substance forming a pattern or an opaque frame on the document or parts of it.

Le film protecteur conforme à l'invention peut être facilement adapté pour couvrir et protéger une ou des surfaces de formes déterminées ; il suffit que la ou les impressions au moyen du ou des mélanges liquides polymérisables, puis l'impression au moyen de la matière adhésive soient réalisées sur une ou des portions de la feuille-support de formes correspondant à celles des surfaces à protéger. Il est à noter que le procédé de l'invention permet de réaliser des produits de protection propres à couvrir de grandes surfaces, et ce, à un coût réduit compte tenu de l'extrême minceur du film de polyuréthane et donc des faibles quantités de matières premières utilisées.The protective film according to the invention can be easily adapted to cover and protect one or more surfaces of determined shapes; it suffices that the impression (s) by means of the polymerizable liquid mixture (s), then the impression by means of the adhesive material are carried out on one or portions of the support sheet of shapes corresponding to those of the surfaces to be protected. It should be noted that the process of the invention makes it possible to produce protective products suitable for covering large areas, at a reduced cost, taking into account the extreme thinness of the polyurethane film and therefore the low quantities of materials. first used.

Par ailleurs, il est possible le cas échéant de doser le pouvoir collant de la couche adhésive en réalisant l'impression de celle-ci sur une pluralité de zones séparées conformément au procédé décrit dans la demande de brevet FR no 86.05039 aux noms des demandeurs. On obtient alors une trame adhésive dont le pouvoir collant est aisément ajustable par un réglage de la densité et/ou de l'étendue des zones adhésives imprimées.Furthermore, it is possible where appropriate to assay the tackiness of the adhesive layer by carrying out the printing thereof on a plurality of separate areas according to the method described in patent application FR No. 86.05039 in the name of applicants . An adhesive screen is then obtained, the adhesive power of which is easily adjustable by adjusting the density and / or the extent of the printed adhesive zones.

Des exemples de réalisation de l'invention sont décrits dans la description qui suit en référence aux dessins annexés ; sur ces dessins :

  • - les figures 1a, 1b, 1 illustrent, à échelle très dilatée, les étapes du procédé de réalisation d'un produit de protection conforme à l'invention, à film monocouche,
  • - les figures 2a, 2b et 2c illustrent l'utilisation de ce produit,
  • - les figures 3a, 3b, 3c, 3d et 3e illustrent, à échelle très dilatée, les étapes du procédé de fabrication d'un produit de protection à film multicouche.
Examples of embodiments of the invention are described in the description which follows with reference to the accompanying drawings; on these drawings:
  • FIGS. 1a, 1b, 1 illustrate, on a very expanded scale, the steps of the process for producing a protection product according to the invention, with a monolayer film,
  • - Figures 2a, 2b and 2c illustrate the use of this product,
  • - Figures 3a, 3b, 3c, 3d and 3e illustrate, on a very expanded scale, the steps of the manufacturing process for a multilayer film protection product.

Le procédé illustré à titre d'exemple est mis en oeuvre sur des machines d'impression sérigraphique, en particulier sur des machines traditionnelles à claquoir (écran articulé) ou sur des machines à écran à soulèvement intégral (écran mobile en translation). Dans le cas ci-après décrit où les impressions ont une épaisseur de l'ordre de 5 à 10 gm (microns), les deux types de machines peuvent être utilisés indifféremment. Dans le cas où des épaisseurs plus importantes seraient souhaitées (entre 10 et 50 µrn (microns), l'on préférera utiliser le second type de machine qui permet d'obtenir des impressions plus épaisses en une seule passe ; bien entendu, le premier type peut également être utilisé en plusieurs passes.The method illustrated by way of example is implemented on screen printing machines, in particular on traditional snap-on machines (hinged screen) or on machines with integral lifting screen (screen movable in translation). In the case described below where the prints have a thickness of the order of 5 to 10 gm (microns), the two types of machine can be used interchangeably. In the case where greater thicknesses are desired (between 10 and 50 µrn (microns), we prefer to use the second type of machine which allows thicker prints to be obtained in a single pass; of course, the first type can also be used in several passes.

Le produit à film monocouche visé aux figures (1 a-lc) comprend une feuille-support transparente 1 (figure 1a) du type dit non adhérent, c'est-à-dire propre à ne développer que de faibles forces de liaison avec la plupart des polymères. Par exemple, cette feuille-support peut être une feuille de polystyrène d'un grammage de l'ordre de 120 g/m2.The monolayer film product referred to in Figures (1 a-lc) comprises a transparent support sheet 1 (Figure 1a) of the so-called non-adherent type, that is to say capable of developing only weak bonding forces with the most polymers. For example, this support sheet can be a polystyrene sheet with a grammage of the order of 120 g / m2.

Cette feuille-support 1 est choisie de taille dépassant celle de la surface à protéger.This support sheet 1 is chosen to be larger than that of the surface to be protected.

Elle est placée sur le plateau de la machine sérigraphique, et l'écran de celle-ci est garni d'un mélange liquide préalablement préparé à partir d'un polyol hydroxylé et d'un isocyanate.It is placed on the plate of the screen printing machine, and the screen thereof is filled with a liquid mixture previously prepared from a hydroxylated polyol and an isocyanate.

Ce mélange peut notamment être préparé en ajoutant deux doses de résine polyacrylique hydroxylée ou de résine polyester hydroxylée, ou de résine polyether hydroxylée à bas poids moléculaire, et une dose de polyisocyanate trifonctionnel aliphatique ou aromatique (par exemple, résine polyacrylique "réf. U8560" et héxaméthylène diisocyanate trimérisé "réf. U8580", vendus par le "Laboratoire CHIMITEC").This mixture can in particular be prepared by adding two doses of hydroxylated polyacrylic resin or hydroxylated polyester resin, or of low molecular weight hydroxylated polyether resin, and a dose of aliphatic or aromatic trifunctional polyisocyanate (for example, polyacrylic resin "ref. U8560" and trimerized hexamethylene diisocyanate "ref. U8580", sold by the "CHIMITEC Laboratory").

La quantité de mélange étalée sur l'écran sérigraphique est ajustée pour correspondre à une épaisseur de 8 à 10 microns.The quantity of mixture spread on the screen printing screen is adjusted to correspond to a thickness of 8 to 10 microns.

Après impression sur la feuille-support 1, le mélange polymérise et donne un mince film transparent de polyuréthane 2. L'impression est effectuée selon une forme correspondant à celle de la surface à protéger, par exemple rectangulaire dans le cas schématisé aux figures 2a, 2b, 2c visant le protection de cartes d'identité.After printing on the support sheet 1, the mixture polymerizes and gives a thin transparent polyurethane film 2. The printing is carried out in a shape corresponding to that of the surface to be protected, for example rectangular in the case shown diagrammatically in FIGS. 2a, 2b, 2c for the protection of identity cards.

Lors d'une production en série, la machine sérigraphique est nettoyée chaque heure pour éviter un colmatage de l'écran.During serial production, the screen printing machine is cleaned every hour to prevent screen clogging.

La feuille-support 1 et son impression polyuréthane 2 sont ensuite laissées à l'air libre afin de permettre à la polymérisation de commencer. La durée totale de celle-ci est de plusieurs jours (de l'ordre de 8 à 10 jours).The support sheet 1 and its polyurethane print 2 are then left in the open air in order to allow the polymerization to start. The total duration of this is several days (of the order of 8 to 10 days).

Avant d'atteindre cette polymérisation complète, l'ensemble est replacé sur la machine sérigraphique pour effectuer une nouvelle impression au-dessus du film 2 au moyen d'une matière adhésive transparente. Selon les conditions de température, on laissera le film polymériser entre 3 et 36 heures et de préférence 4 ou 5 heures environ. Ces délais permettent de garantir que le film est suffisamment sec et consistant pour subir une impression mais avec une polymérisation encore incomplète pour permettre une meilleure adhésion de la nouvelle impression. Celle-ci sera par exemple effectuée en utilisant une matière adhésive acrylique du type vendu par "TIFLEX" sous la référence "adhésif acrylique". Cette impression est réalisée sur toute la surface du film 2 afin de le revêtir d'une couche adhésive transparente 3 (figure 1b) dont l'épaisseur est similaire à celle du film (comprise entre 5 et 50 microns et, en l'exemple de l'ordre de 8 à 10 microns).Before reaching this complete polymerization, the assembly is replaced on the screen printing machine to make a new impression above the film 2 by means of a transparent adhesive material. Depending on the temperature conditions, the film will be allowed to polymerize between 3 and 36 hours and preferably approximately 4 or 5 hours. These periods make it possible to guarantee that the film is sufficiently dry and consistent to undergo printing but with a polymerization still incomplete to allow better adhesion of the new printing. This will for example be carried out using an acrylic adhesive material of the type sold by "TIFLEX" under the reference "acrylic adhesive". This printing is carried out on the entire surface of the film 2 in order to coat it with a transparent adhesive layer 3 (FIG. 1b) whose thickness is similar to that of the film (between 5 and 50 microns and, in the example of 8 to 10 microns).

L'ensemble est ensuite couvert par une feuille protectrice siliconée 4 (figure 1c) dont le grammage peut être de l'ordre de 145 gr/m2.The whole is then covered by a silicone protective sheet 4 (FIG. 1c), the grammage of which can be of the order of 145 gr / m2.

Le produit de protection ainsi obtenu peut être stocké et distribué sans précaution particulière.The protection product thus obtained can be stored and distributed without special precautions.

Aux figures 2a, 2b et 2c, on a schématisé .une application de l'invention pour la protection de cartes d'identité. Cette protection peut être effectuée par l'administration chargée d'établir ces cartes, après apposition par le titulaire de sa signature et, le cas échéant, d'empreintes digitales, et ceci au moment même où la carte d'identité lui est remise.In Figures 2a, 2b and 2c, there is shown schematically an application of the invention for the protection of identity cards. This protection may be carried out by the administration responsible for establishing these cards, after the holder has affixed his signature and, where appropriate, fingerprints, at the same time as the identity card is given to him.

Le produit de protection est schématisé en perspective à la figure 2a, la feuille protectrice siliconée 4 étant en cours de retrait.The protection product is shown diagrammatically in perspective in FIG. 2a, the silicone protective sheet 4 being removed.

Après retrait de cette feuille protectrice, le produit est appliqué sur la carte d'identité (figure 2b), les impressions 2 et 3 de polyuréthane et matière adhésive ayant la forme d'un rectangle de taille correspondant à celui de cette carte. Ces impressions sont mises en correspondance avec la surface de la carte et l'opérateur exécute une pression qui amène la couche adhésive 3 à adhérer sur la carte avec transfert simultané du film 2.After removing this protective sheet, the product is applied to the identity card (FIG. 2b), the impressions 2 and 3 of polyurethane and adhesive material having the shape of a rectangle of size corresponding to that of this card. These prints are matched to the surface of the card and the operator applies pressure which causes the adhesive layer 3 to adhere to the card with simultaneous transfer of the film 2.

Il suffit ensuite de détacher la feuille-support 1 (figure 2c) et la carte d'identité est protégée.Then just detach the support sheet 1 (Figure 2c) and the identity card is protected.

Les essais sont montré que le mince film 2, une fois qu'il a adhéré au document grâce à la couche adhésive 3, est impossible à séparer de celui-ci. En raison de son excellente résistance mécanique, il ne peut être localement gratté sans abîmer le document. De plus, des essais avec des solvants ou diluants n'ont pas permis d'en trouver un capable d'attaquer le film sans détériorer le document en papier. On obtient ainsi un document extrêmement difficile à falsifier.The tests are shown that the thin film 2, once it has adhered to the document thanks to the adhesive layer 3, is impossible to separate from it. Due to its excellent mechanical resistance, it cannot be locally scratched without damaging the document. In addition, tests with solvents or diluents did not make it possible to find one capable of attacking the film without damaging the paper document. This produces a document that is extremely difficult to forge.

Il est à noter que le film protecteur est peu apparent et ne modifie par sensiblement la souplesse de la carte.It should be noted that the protective film is not very visible and does not significantly modify the flexibility of the card.

Par ailleurs, les figures 3a-3e illustrent (à échelle plus grande) la fabrication d'un produit de protection à film polyuréthane multicouche.Furthermore, FIGS. 3a-3e illustrate (on a larger scale) the manufacture of a protection product with a multilayer polyurethane film.

La première étape (figures 3a) est similaire à la première étape du procédé déjà décrit et consiste à imprimer sur une feuille-support en polystyrène 5 une couche transparente de polyuréthane 6 au moyen d'un mélange polymérisable identique à celui déjà décrit.The first step (FIGS. 3a) is similar to the first step of the process already described and consists in printing on a polystyrene support sheet 5 a transparent layer of polyurethane 6 by means of a polymerizable mixture identical to that already described.

Avant la fin de la polymérisation de ce mélange, c'est-à-dire dans un délai compris entre 3 et 36 heures après cette impression, une impression intercalaire discontinue 7 de dessins, motifs ou trames est effectuée sur la première impression (figure 3b). Un délai de l'ordre de 4 à 5 heures donne de bons résultats (impression initiale suffisamment consistante pour permettre l'impression intercalaire, tout en autorisant une adhésion étroite des couches en raison des phénomènes de polymérisation simultanés à leur interface).Before the polymerization of this mixture has ended, that is to say within a period of between 3 and 36 hours after this printing, a discontinuous intermediate printing 7 of drawings, patterns or screens is carried out on the first printing (FIG. 3b ). A delay of the order of 4 to 5 hours gives good results (initial printing sufficiently consistent to allow intermediate printing, while allowing close adhesion of the layers due to the simultaneous polymerization phenomena at their interface).

Cette impression intercalaire 7 est réalisée avec une résine de base similaire à laquelle à été ajoutée une substance colorée entre 2 et 50 % en poids, le polyisocyanate étant ensuite mélangé. Par exemple, selon les effets recherchés, on peut ajouter une des substances suivantes se présentant sous la forme de fine poudre :

  • - substance à base de terres et métaux rares, vendue par "CHIMITEC" sous la référence "Lumiton fluo U.V. codes" (entre 2 et 25 % en poids), afin de fournir des motifs invisibles à la lumière solaire, devenant fluorescents sous radiation ultraviolette,
  • - substance à base de colorants organiques fluorescents possédant une longue série de doubles liaisons sous forme cyclique ou benzénique, vendue par "CHIMITEC" sous la référence "Lumiton fluo LJ" (entre 25 % et 50 % en poids), afin de fournir des motifs fluorescents à la lumière solaire, possédant une fluorescence intense sous radiation ultraviolette avec changement de couleur,
  • - pigments opaques à base d'oxyde de titane ou de noir de carbone (de 5 % à 25 % en poids),
  • - pigments organiques transparents à base d'ophta- locyanine (bleu) ou de jaune "HANSA" (entre 5 % et 25 % en poids).
This intermediate printing 7 is carried out with a similar base resin to which has been added a colored substance between 2 and 50% by weight, the polyisocyanate then being mixed. For example, depending on the desired effects, we can add a the following substances in the form of a fine powder:
  • - substance based on rare earths and metals, sold by "CHIMITEC" under the reference "Lumiton fluo UV codes" (between 2 and 25% by weight), in order to provide patterns invisible to sunlight, becoming fluorescent under ultraviolet radiation ,
  • - substance based on fluorescent organic dyes having a long series of double bonds in cyclic or benzene form, sold by "CHIMITEC" under the reference "Lumiton fluo LJ" (between 25% and 50% by weight), in order to provide patterns fluorescent in sunlight, having intense fluorescence under ultraviolet radiation with color change,
  • - opaque pigments based on titanium oxide or carbon black (from 5% to 25% by weight),
  • - transparent organic pigments based on ophthalocyanin (blue) or "HANSA" yellow (between 5% and 25% by weight).

Avant polymérisation complète de cette impression intercalaire, on réalise une seconde impression 8 identique à l'impression 6 pour obtenir une nouvelle couche transparente de polyuréthane (figure 3c). Cette impression est réalisée dans le même délai que précédemment (entre 3 et 36 heures et de préférence de 4 à 5 heures après l'impression intercalaire).Before complete polymerization of this intermediate printing, a second printing 8 is carried out identical to printing 6 in order to obtain a new transparent layer of polyurethane (FIG. 3c). This printing is carried out in the same time as previously (between 3 and 36 hours and preferably 4 to 5 hours after the interlayer printing).

Au terme de la polymérisation des trois couches 6, 7 et 8, on obtient un film composite de polyurétha- ne avec motif ou trame intégré, les couches n'étant plus séparables. Ce film multicouche peut notamment avoir une épaisseur de l'ordre de 8 à 20 microns.After the polymerization of the three layers 6, 7 and 8, there is obtained a composite film polyurétha - with no pattern or integrated frame, wherein the layers are not separable. This multilayer film may in particular have a thickness of the order of 8 to 20 microns.

Une impression de matière adhésive transparente 9 est ensuite réalisée comme précédemment (figure 3d). Cette impression est de préférence confectionnée ayant polymérisation complète de la couche 8 dans un délai compris entre 3 et 36 heures et de préférence de l'ordre de 4 à 5 heures.Printing of transparent adhesive material 9 is then carried out as previously (FIG. 3d). This impression is preferably made having complete polymerization of the layer 8 within a period of between 3 and 36 hours and preferably of the order of 4 to 5 hours.

L'ensemble est ensuite couvert par une feuille protectrice siliconée 10 analogue à celle du produit précédemment décrit.The assembly is then covered by a silicone protective sheet 10 similar to that of the product previously described.

Le produit de protection ainsi obtenu peut être stocké et distribué sans précaution particulière. Son utilisation est similaire à celle déjà décrite du produit à film polyuréthane monocouche. Il est à noter que, le cas échéant, plusieurs impressions intercalaires peuvent être superposées grâce à des passes successives sur la machine (avec un délai entre passes compris entre 3 et 36 heures et de préférence de l'ordre de 4 à 5 heures).The protection product thus obtained can be stored and distributed without special precautions. Its use is similar to that already described for the product with a single-layer polyurethane film. It should be noted that, if necessary, several intermediate prints can be superimposed by successive passes on the machine (with a delay between passes of between 3 and 36 hours and preferably of the order of 4 to 5 hours).

Claims (16)

1. Process for bringing about a protective product with a protective film capable of being transferred in the cold state by simple pressure, which can be used for covering end protecting on the surface a document or other object, characterised in that it consists in producing on a non-adhesive support foil (1) an imprint (2) by means of a liquid polymerisable two-component mixture containing a hydroxylated polyol and an isocyanate or polhisocyanate so as to cause polymerisation of the mixture in situ, leading to a thin transparent polyurethane film, and in covering said film with a transparent adhesive layer (3).
2. Process for bringing about a protective product with a protective film capable of being transferred in the cold state by simple pressure and used for covering and protecting on the surface a document or other object, characterised in that it consists:
- in bringing about on a non-adhesive support foil a first continuous imprint with the aid of a liquid, polymerisable twocomponent mixture containing a hydroxylated polyol and an isocyanate or polyisocyanate in such a manner as to cause polymerisation of the mixture in situ, leading to a first transparent polyurethane layer,
- in bringing about, prior to complete polymerisation of said first imprint, at least one intermediate imprint corresponding to a motif or screen with the aid of a liquid, polymerisable two-component mixture containing a hydroxylated polyol and an isocyanate or polyisocyanate with the addition of a coloured substance from the following group: substance fluorescent under radiation, in particular ultraviolet radiation, and invisible in light, substance fluorescent under radiation, in particular ultraviolet radiation, and visible in light, or opaque pigment, in such a manner as to cause polymerisation of said mixture in situ, leading to a discontinuous intermediary polyurethane layer,
- in bringing about, prior to complete polymerisation of the intermediate imprint, a second continuous imprint with the aid of a liquid, polymerisable two-component mixture based on hydroxylated polyol and isocyanate or polyisocyanate, in such a manner as to cause polymerisation of the mixture in situ, leading to a second transparent polyurethane layer,
- and in covering the second imprint with e transparent adhesive layer.
3. Process according to claim 2, in which:
- the intermediate imprint is applied 3 to 36 hours after the first imprint,
- the second imprint is applied 3 to 36 hours after the intermediate imprint.
4. Process according to one of claims 1, 2 or 3, in which the liquid, polymerisable mixture used for each imprint is a mixture of hydroxylated polyacrylic resin or hydroxylated polyester resin or hydroxylated polyether resin and aliphatic or aromatic polyisocyanate.
5. Process according to claim 4, in which the liquid, polymerisable mixture used for each imprint is prepared by mixing from 1.8 to 2.2 doses of resin per dose of isocyanate or polyisocyanate.
6. Process according to claims 2 and 5 jointly, in which the liquid, polymerisable mixture used for each intermediate imprint contains, in relation to the weight of the resin, from 2 to 50 per cent of coloured substance.
7. Process according to one of claims 1, 2, 3, 4, 5 or 6, characterised in that each imprint carried out with the aid of the liquid, polymerisable mixture is brought about by silk-screen printing or gravure printing.
8. Process according to claim 4, characterised in that the imprint or imprints by silk-screen or gravure printing are brought about so as to produce on support foil (1) a film (2) having a total thickness from 5 to 50 microns.
9. Process according to one of claims 7 or 8, characterised in that the transparent adhesive layer is produced 3 to 36 hours after the last imprint, by bringing about a film imprint, in particular by silk-screen or gravure printing, with the aid of transparent adhesive material.
10. Process according to claim 9, in which the adhesive material used is of acrylic type.
11. Process according to one of claims 9 or 10, in which the imprint produced with the aid of adhesive material is brought about on a plurality of separate zones, with a view to producing a discontinuous adhesive layer of adjustable adhesive power.
12. Process according to one of the preceding claims, in which a siliconated protective foil (4) is arranged on top of adhesive layer (3).
13. Protective product such as to enable, by transfer in the cold state by simple pressure, a document or other object to be covered and protected on the surface, characterised in that it comprises, on the one hand, a thin polyurethane film (2) imprinted on a non-adhesive support foil (1) and produced by means of a two-component mixture, and, on the other hand, a transparent adhesive layer (3) covering said film and surmounted by a siliconated protective foil (4).
14. Protective product according to claim 13, in which the thin film is a single-layer transparent film.
15. Protective product according to claim 13, in which the thin film is a multi-layer film, comprising two transparent polyurethane layers situated at either side of a polyurethane layer containing a coloured substance.
16. Protective product according to one of claims 13, 14 or 15, in which the adhesive layer is an acrylic layer imprinted on the polyurethane film.
EP87202288A 1986-11-27 1987-11-23 Method for manufacturing a transfer product with a protection layer, and product obtained for the protection of documents or other produce Expired - Lifetime EP0271941B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87202288T ATE56667T1 (en) 1986-11-27 1987-11-23 PROCESS FOR MANUFACTURE OF TRANSMISSION PRODUCTS WITH A PROTECTION LAYER AND OBTAINED PRODUCT FOR DOCUMENT PROTECTION.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8616707A FR2607435B1 (en) 1986-11-27 1986-11-27 PROCESS FOR PRODUCING A PRODUCT WITH TRANSFERABLE PROTECTIVE FILM AND PRODUCT OBTAINED FOR THE PROTECTION OF DOCUMENTS OR THE LIKE
FR8616707 1986-11-27

Publications (2)

Publication Number Publication Date
EP0271941A1 EP0271941A1 (en) 1988-06-22
EP0271941B1 true EP0271941B1 (en) 1990-09-19

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP87202288A Expired - Lifetime EP0271941B1 (en) 1986-11-27 1987-11-23 Method for manufacturing a transfer product with a protection layer, and product obtained for the protection of documents or other produce

Country Status (14)

Country Link
US (1) US5232527A (en)
EP (1) EP0271941B1 (en)
AT (1) ATE56667T1 (en)
DE (1) DE3765096D1 (en)
DZ (1) DZ1144A1 (en)
EG (1) EG18570A (en)
ES (1) ES2017709B3 (en)
FR (1) FR2607435B1 (en)
GR (1) GR3001094T3 (en)
MA (1) MA21112A1 (en)
OA (1) OA08780A (en)
PT (1) PT86222B (en)
TN (1) TNSN87133A1 (en)
ZA (1) ZA878949B (en)

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US5788796A (en) * 1994-05-20 1998-08-04 Minnesota Mining And Manufacturing Decal assembly and method of making same
CA2215304C (en) * 1995-03-13 2004-06-22 Portals Limited Security paper
FR2732137B1 (en) * 1995-03-23 1997-05-30 Moisand Jean Claude OPTICAL TRACK SECURITY CARD
US6200666B1 (en) * 1996-07-25 2001-03-13 3M Innovative Properties Company Thermal transfer compositions, articles, and graphic articles made with same
FR2762336B1 (en) 1997-04-21 1999-06-11 Francois Trantoul METHOD FOR MANUFACTURING A NON-REPRODUCIBLE PATTERNED FILM BY OPTICAL READING FOR THE PROTECTION OF DOCUMENTS
US6127050A (en) * 1997-05-22 2000-10-03 Fromson; Howard A. Archival imaging medium and method therefor
FR2785061B1 (en) * 1998-10-23 2000-12-15 Francois Trantoul METHOD FOR PRODUCING ANY PHOTOLUMINESCENT PRINTED POLYCHROMATIC IMAGE, IMAGE OBTAINED AND APPLICATIONS
FR2793726B1 (en) * 1999-05-21 2001-08-03 Francois Trantoul METHOD AND PRODUCT FOR PROTECTING AN OBJECT BY A SECURITY PRINT WITH A SOLUBLE BINDER, METHOD FOR MANUFACTURING THIS PRODUCT AND OBJECT OBTAINED
US20020163179A1 (en) * 2001-05-01 2002-11-07 Dubner Andrew D. Transparent tamper-indicating data sheet
FR2830115B1 (en) * 2001-09-21 2003-11-28 Francois Trantoul ANTIFALSIFICATION VIGNETTE FOR LAYING VARIABLE INSCRIPTIONS ON A MARKING MEDIUM, PROCESS AND MARKED MEDIUM OBTAINED
FR2834484B1 (en) 2002-01-09 2004-09-03 Francois Trantoul METHOD FOR PRODUCING A TRANSPARENT TRANSFERABLE SECURITY FILM PROTECTIVE DEVICE WITH SHORT ULTRAVIOLET
US6875497B2 (en) 2002-05-08 2005-04-05 Flexcon Company, Inc. Multilayer composite for the dry transfer of graphics to receptive substrates
FR2840431B1 (en) 2002-05-29 2004-09-03 Francois Trantoul METHOD AND DEVICE FOR PROTECTING READING INSTRUCTIONS
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US20070029787A1 (en) * 2005-07-14 2007-02-08 Loftin Robert L Iii Apparatuses and methods for protecting confidential information
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Also Published As

Publication number Publication date
MA21112A1 (en) 1988-07-01
OA08780A (en) 1989-03-31
DE3765096D1 (en) 1990-10-25
EG18570A (en) 1993-08-30
GR3001094T3 (en) 1992-04-17
PT86222A (en) 1988-12-15
EP0271941A1 (en) 1988-06-22
FR2607435A1 (en) 1988-06-03
FR2607435B1 (en) 1989-04-07
US5232527A (en) 1993-08-03
ZA878949B (en) 1988-05-24
ATE56667T1 (en) 1990-10-15
PT86222B (en) 1993-08-31
DZ1144A1 (en) 2004-09-13
ES2017709B3 (en) 1991-03-01
TNSN87133A1 (en) 1990-01-01

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