EP1765587B1 - Method for producing a metallic coating in certain areas of a substrate, transfer film and use thereof - Google Patents

Method for producing a metallic coating in certain areas of a substrate, transfer film and use thereof Download PDF

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Publication number
EP1765587B1
EP1765587B1 EP05761989A EP05761989A EP1765587B1 EP 1765587 B1 EP1765587 B1 EP 1765587B1 EP 05761989 A EP05761989 A EP 05761989A EP 05761989 A EP05761989 A EP 05761989A EP 1765587 B1 EP1765587 B1 EP 1765587B1
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EP
European Patent Office
Prior art keywords
layer
transfer
process according
metal layer
soluble
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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.)
Not-in-force
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EP05761989A
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German (de)
French (fr)
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EP1765587A1 (en
Inventor
Ludwig Brehm
Heinrich Wild
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Leonhard Kurz Stiftung and Co KG
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Leonhard Kurz Stiftung and Co KG
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Publication of EP1765587A1 publication Critical patent/EP1765587A1/en
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Classifications

    • 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
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/373—Metallic materials
    • 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
    • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B44C1/17—Dry transfer
    • B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
    • B44C1/1716—Decalcomanias provided with a particular decorative layer, e.g. specially adapted to allow the formation of a metallic or dyestuff layer on a substrate unsuitable for direct deposition
    • 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
    • B42D25/40—Manufacture
    • B42D25/405—Marking
    • B42D25/43—Marking by removal of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C3/00—Processes, not specifically provided for elsewhere, for producing ornamental structures
    • B44C3/005—Removing selectively parts of at least the upper layer of a multi-layer article
    • B42D2033/10—

Definitions

  • the invention relates to a method for producing a zone-wise metallization on a carrier substrate, wherein the carrier substrate is at least partially provided with a soluble, colored first layer which is provided over its entire surface with a metal layer on its side facing away from the carrier substrate.
  • the invention further relates to a transfer film which comprises a carrier substrate and a transfer layer with a zone-wise metallization, wherein the carrier substrate is formed as a carrier film and the transfer layer has at least one partially arranged colored first layer and a metal layer arranged congruently to the first layer, as well as the latter Use.
  • Such a method and such a transfer sheet are known from WO 98/50241 known.
  • a composite film structure disclosed in some areas Having reflective metal layer which is formed congruent or accurate register on areas of a lacquer layer.
  • a carrier film is coated with a soluble, optionally colored first lacquer layer and the side of the first lacquer layer facing away from the carrier film is covered with a reflective metal layer.
  • portions of the metal layer are to be removed by either coating a base in a desired pattern on the metal layer, or coating a base-insoluble layer in a pattern on the metal layer, and then coating a base onto the insoluble layer and the exposed areas of the metal layer Metal layer is applied.
  • the base should now dissolve through the metal layer through the soluble first coat of paint.
  • the reason for this seems to be due to the deposited metal layer which is usually formed by vapor deposition or sputtering on the first lacquer layer typically via a PVD process (P hysical V apour D eposition).
  • PVD process Physical V apour D eposition
  • a method is described here in which a soluble paint is partially printed with a curing agent, the curing agent and free areas of the paint are coated with a metal layer and then the paint in the areas where no curing agent was present including the arranged thereon Dissolve metal layer to produce a partial metallization of the carrier substrate registering to the cured areas of the paint.
  • these two methods last described in the case of a large number of paints cause the solubility of the lacquer layer after metallization to be markedly worsened, so that a defined detachment of the lacquer layer areas provided directly with the metal layer is made difficult or even impossible ,
  • a soluble first color or lacquer layer is applied over its entire surface to a carrier substrate and is partially covered with a second color or lacquer layer which contains a hardener for the first layer.
  • the areas of the first layer in which the second layer was absent are dissolved by a solvent, so that areas with two register-accurate color layers are formed.
  • DE 34 30 111 C1 discloses a foil with a decorative metal layer and a method for its production.
  • a soluble coating on a carrier film is partially printed with a curing agent or a Aushärtlack containing a curing agent in excess.
  • the hardener diffuses into the underlying, soluble paint and hardens it.
  • a concentration gradient of the hardener is formed in the soluble paint, wherein in the direction of the carrier film, the hardener concentration decreases and thereby a locally different degrees of hardening of the soluble layer is effected.
  • uncured areas of the soluble lacquer may be present in the region of the carrier film which, during the washing of the Areas that have not been printed with curing agent, also be partially or completely replaced with.
  • the curing of the soluble paint in the region of the support film is sufficient so far that solubility is no longer present, the non-uniform hardening of the soluble paint due to the concentration gradient has an unfavorable effect on its mechanical properties.
  • a residue of the pure curing agent or the Aushärtlack
  • the regions of the first layer which are to be dissolved again are not coated directly with the metal layer at any point, so that there is no change in the solubility of the first layer due to the coating with the metal layer.
  • the regions of the first layer which are to be redissolved are, according to the invention, brought into direct contact with the second layer, which has an additive which is adapted to a hardener contained in the first layer.
  • the additive in the second layer inactivates the hardener in the first layer before the hardener becomes active and hardens the first layer.
  • the second layer and exposed portions of the first layer are coated with a metal layer, which is preferably formed in a PVD process such as vapor deposition or sputtering.
  • the second layer and the regions of the first layer, in which the hardener was inactivated dissolved by means of the liquid and removed. It also becomes the part of the metal layer removed, which is arranged directly on the second layer, and thus a partial metallization is formed on the carrier substrate.
  • the partial metallization is located where the first layer was directly coated and cured with the metal layer.
  • the at least one third layer present in case b) is insoluble and allows additional decorative effects. In this case, the optical impressions of the first and the third layer can overlap and also the third layer can be provided at least in regions with the metal layer.
  • the method according to the invention enables a reliable detachment of the uncured regions of the first layer and the regions of the metal layer arranged thereon, it being possible to reproducibly produce metal layer regions having defined dimensions and sharp edges.
  • the first lacquer layer is divided into hardened and uncured regions, and on the other hand, the regions of the first lacquer layer to be hardened are additionally directly coated with the metal layer, which leads to the above-described reduction of the solubility of the first lacquer layer.
  • This double influence on the first lacquer layer can be seen as the cause for the high edge sharpness of the formed metallization areas and for the extremely high registration accuracy of the hardened areas of the first lacquer layer and the areas of the metal layer arranged thereon.
  • the hardened regions of the first layer remaining under the regions of the metal layer have a uniform degree of cure over their surface and, seen in cross-section, over their layer thickness, since the hardener is uniform in the material even in the formation of the first layer is distributed to form the first layer.
  • the uniform hardening of the first layer can be determined, for example, by the fact that the abrasion, the solubility, the refractive index, the molecular weight or a Molecular weight of the first layer - seen in cross-section - determined for different layer depths and compared.
  • the degree of hardening of the first layer for example via the vapor pressure of polymers in the first layer or by determining the deformability of the first layer - also seen in cross section - for different layer depths and to compare them.
  • no different measured values can be ascertained in the resulting, hardened first layer.
  • the ink is formed alkaline by means of sodium hydroxide or potassium hydroxide, wherein the sodium hydroxide or potassium hydroxide forms the additive. It has been found that these additives from the second layer reliably inactivate an aziridine-based or polyimine-based hardener in the first layer and thus prevent the hardening of the first layer in a reproducible area. Such hardeners cure the first layer only at temperatures above about 80 ° C accelerated. At room temperature, the curing is very slow, so that inactivation of the curing agent by the additive in the ink can be done, especially if this is applied "inline" in a subsequent printing on the first layer.
  • the printing ink for forming the second layer is preferably added with a coloring filler or pigment to the arrangement and training the formed second layer in a simple manner to undergo a visual inspection. It has proven useful to add barium sulfate, titanium oxide or zinc sulfide to the ink in order to make them visible.
  • the object is achieved for the transfer film, in particular a hot stamping foil, by hardening the first layer by means of an aziridine-based or polyimine-based hardener, the first layer having cured uniformly over its layer thickness.
  • the first layer is preferably formed by an alkali-soluble lacquer, preferably based on polyacrylic acid or styrene-maleic anhydride.
  • a layer thickness in the range of 0.7 to 2 ⁇ m is preferably selected.
  • the additive of the second layer can reliably inactivate the hardener in the first layer over the entire layer thickness of the first layer. It has proven useful to form the second layer with a thickness in the range of 0.8 to 3 microns.
  • the first layer is transparent in order to make visible and fully emphasize the metal mirror through the first layer.
  • the first layer may consist of several transparent layers whose optical effect influences each other.
  • the carrier film and / or the transfer layer of the transfer film are at least partially transparent.
  • partially transparent transfer layers which are applied to a document of value, still allow the surface of the document of value to be recognized and to achieve additional protection against counterfeiting.
  • the transfer layer has an adhesive layer, wherein the adhesive layer is arranged on the side of the transfer layer facing away from the carrier film.
  • the adhesive layer is arranged on the side of the transfer layer facing away from the carrier film.
  • the at least one third layer which may be provided in the transfer layer, it is possible to achieve special decorative effects if this is made opaque in color and / or colored transparent.
  • a wax-like separating layer is arranged between the carrier film and the transfer layer.
  • Such separating layers usually have a thickness in the range of 0.001 to 0.1 ⁇ m.
  • the carrier film preferably made of plastics such as PI, PP, PE, PET, PPS, LCP, PEN, PA, PVC, paper, fabrics or metal foil, thereby dissolves easily under pressure and temperature during hot stamping of the transfer layer and allows accurate and complete application to a material to be embossed.
  • a flexible film material having a thickness in the range from 5 to 700 .mu.m, preferably in the range from 12 to 50 .mu.m, as the carrier substrate, so that this can be provided on a supply roll and processed endlessly. It is particularly advantageous in this case if the carrier substrate is transported from roll to roll to form the zone-wise metallization. This means that the carrier substrate withdrawn from a first supply roll, the process of the invention, optionally also subjected to further process steps, and finally can be wound onto a second supply roll, which is further processed. Further process steps include, for example, embossing processes, temperature treatments or irradiation.
  • the metal layer is designed to be reflective, preferably reflective and reflective. This further enhances the decorative effect of the area-wise metallization.
  • the metal layer is formed from one of the metals aluminum, chromium, copper, nickel, iron, titanium, silver, gold or an alloy of two or more of these metals. These metals can produce a specularly reflective metal layer.
  • the metal layer is preferably formed by vapor deposition or cathode sputtering, since these methods can be carried out in a continuous and thus particularly economical process.
  • the metal layer (s) in a thickness in the range of 10 to 100 nm.
  • transfer film according to the invention for the formation of security elements on data carriers, in particular value documents such as identity cards, cards or banknotes, of components or decorative elements, in particular in architecture or other technical fields, of packaging materials, in particular in the pharmaceutical or food industry or of components in the Electrical or electronics industry is ideal.
  • FIG. 1a shows in cross-section as a support film formed carrier substrate 1, which is coated with an alkali-soluble, colored paint based on styrene-maleic anhydride (SMA) as a first layer 2.
  • SMA styrene-maleic anhydride
  • the lacquer for forming the first layer had the following composition: ethanol 3200g ethyl acetate 3100g n-butanol 100 g SMA resin (MW approx. 200000, acid number approx. 250) 1000g Alcohol-soluble cellulose nitrate (standard 30 A) 100 g Complex dye orange 85g Complex dye yellow 38g Aziridine hardener 25g
  • the carrier substrate 1 made of PET has a thickness of 25 .mu.m and the first layer 2 has a thickness of 1 .mu.m.
  • the first layer 2 can be applied over the entire surface or only partially on the carrier substrate 1.
  • the first layer 2 in the present case contains an aziridine-based hardener. Between the carrier substrate 1 and the first layer 2 further lacquer layers, reflective layers or other layers can be arranged, which may have, for example, magnetic properties.
  • On the first layer 2 is partially applied a water-soluble, strongly alkaline printing ink as a second layer 3, which contains sodium hydroxide as an additive and has a thickness of 1.5 microns. The ink was added to titanium oxide to give a highly visible and controllable print result.
  • the printing ink for forming the second layer had the following composition: water 9200G Methylcellulose (low molecular weight) 750g Silica fumed 150g Titanium dioxide (rutile type) 2000g ethanol 1000g n-butanol 600g Caustic soda (50 percent) 2000g
  • a specularly reflective metal layer 4 of aluminum having a thickness of 40 nm covers the second layer 3 and the uncovered areas of the first layer 2.
  • the sodium hydroxide of the second layer 3 inactivates the hardener in the first layer 2 in the areas in which a direct contact between the first layer 2 and the second layer 3 was generated.
  • FIG. 1b shows the carrier substrate 1 from FIG. 1a after dissolving the second layer 3 and uncured areas of the first layer 2 in water. Only in the areas of the first layer 2, which were not covered by the second layer 3, the curing agent became active and led to a hardening of the first layer 2. These areas thus remain on the carrier substrate 1, including the registration areas located directly on it of the metal layer 4, while the uncured portions of the first layer 2 and the portions of the metal layer 4 disposed on the second layer 3 have been removed.
  • FIG. 2a shows a further carrier substrate 1 with a completely applied thereto, water-soluble first layer 2 based on styrene-maleic anhydride according to FIG. 1a containing an aziridine-based hardener. The first layer 2 is colored and transparent. On the first layer 2, a water-insoluble, color-transparent third layer 7 is partially applied.
  • the water-insoluble varnish for forming the third layer had the following Composition on: methyl ethyl ketone 2600g PMMA (high molecular weight, Tg 120 ° C) 500g toluene 2000g Ester-soluble cellulose nitrate (standard 34 E) 1000g cyclohexanone 300g Complex dye red 45g
  • a water-soluble, second layer 3 is arranged, which consists of a strong alkaline ink according to FIG. 1a educated.
  • the second layer 3 contains as additive sodium hydroxide which inactivates the hardener in the first layer 2 in the areas which are in direct contact therewith.
  • the second layer 3 does not affect the third layer 7, so that the third layer 7 for the sodium hydroxide of the second layer 3 forms a barrier layer.
  • a closed metal layer 4 of chromium covers the second layer 3, parts of the first layer 2 and parts of the third layer 7.
  • FIG. 2b shows the carrier substrate 1 from FIG. 2a after dissolving the second layer 3 and uncured areas of the first layer 2 in water.
  • areas of the first layer 2 remain in register with areas of the metal layer 4, uncoated areas of the third layer 7 and areas of the metal layer 4 occupied areas of the third layer 7
  • Variation of the arrangement of the individual layers can be achieved here very different effects.
  • FIG. 3 shows the cross section through a hot stamping foil 10 with areawise metallization.
  • a colorless transparent, insoluble resist layer 8 is arranged, on the regions of the first layer 2 and the metal layer 4 as shown in FIG FIG. 1 b formed, are arranged.
  • An adhesive layer 6 is located on the side facing away from the carrier substrate 1 side of the transfer layer 9. As an adhesive, a heat-sealable adhesive is preferably used.
  • the hot stamping film 10 When hot stamping the hot stamping film 10 is pressed under the action of temperature with the adhesive layer 6 against the material to be embossed and the transfer layer 9 completely or partially, for example in the form of patterns, alphanumeric characters or images transferred.
  • the carrier substrate 1 is separated from the transferred to the embossed material areas of the transfer layer 9.
  • the colorless transparent lacquer layer 8 now forms the surface of the transferred regions of the transfer layer 9 and protects the layer layers arranged underneath, for example against damage or manipulative change.
  • the layer systems shown in the figures can be supplemented by further transparent or opaque layers, whereby various effects can be produced.
  • the first layer 2 can be formed from two or more colored, transparent soluble lacquer layers. Also it is possible to use opaque color layers for structuring or a metal layer which is formed in regions from metals of different colors.

Abstract

The invention concerns a process for the production of a region-wise metallization on a carrier substrate, wherein the carrier substrate is at least region-wise provided with a soluble colored first layer which on its side remote from the carrier substrate is provided over its full area with a metal layer, as well as a transfer film with a region-wise metalization and the use thereof.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung einer bereichsweisen Metallisierung auf einem Trägersubstrat, wobei das Trägersubstrat zumindest bereichsweise mit einer löslichen, farbigen ersten Schicht versehen wird, die auf ihrer dem Trägersubstrat abgewandten Seite vollflächig mit einer Metallschicht versehen wird. Die Erfindung betrifft weiterhin eine Transferfolie, die ein Trägersubstrat und eine Übertragungslage mit einer bereichsweisen Metallisierung umfasst, wobei das Trägersubstrat als eine Trägerfolie ausgebildet ist und die Übertragungslage zumindest eine bereichsweise angeordnete farbige, erste Schicht und eine deckungsgleich zur ersten Schicht angeordnete Metallschicht aufweist, sowie deren Verwendung.The invention relates to a method for producing a zone-wise metallization on a carrier substrate, wherein the carrier substrate is at least partially provided with a soluble, colored first layer which is provided over its entire surface with a metal layer on its side facing away from the carrier substrate. The invention further relates to a transfer film which comprises a carrier substrate and a transfer layer with a zone-wise metallization, wherein the carrier substrate is formed as a carrier film and the transfer layer has at least one partially arranged colored first layer and a metal layer arranged congruently to the first layer, as well as the latter Use.

Ein derartiges Verfahren und eine derartige Transferfolie sind aus der WO 98/50241 bekannt. Hier ist eine Verbundfolienstruktur offenbart, die bereichsweise eine reflektierende Metallschicht aufweist, die deckungsgleich beziehungsweise passergenau auf Bereichen einer Lackschicht gebildet ist. Eine Trägerfolie wird dabei mit einer löslichen, gegebenenfalls farbigen ersten Lackschicht beschichtet und die der Trägerfolie abgewandte Seite der ersten Lackschicht mit einer reflektierenden Metallschicht bedeckt. Nun sollen Bereiche der Metallschicht entfernt werden, indem entweder eine Base in einem gewünschten Muster auf die Metallschicht aufgebracht wird, oder eine in Base unlösliche Schicht in einem Muster auf die Metallschicht aufgebracht wird und anschließend eine Base auf die unlösliche Schicht und die frei gebliebenen Bereiche der Metallschicht aufgetragen wird. Die Base soll nun durch die Metallschicht hindurch die lösliche erste Lackschicht lösen. Es hat sich jedoch als äußerst schwierig erwiesen, die erste Lackschicht auf diesem Wege zuverlässig und in den gewünschten Bereichen vollständig zu lösen. Der Grund hierfür scheint in der aufgebrachten Metallschicht begründet zu sein, welche üblicherweise über ein PVD-Verfahren (Physical Vapour Deposition), meist mittels Aufdampfen oder Kathodenzerstäubung auf der ersten Lackschicht gebildet wird. Dabei kommt es zumindest im Bereich der Oberfläche der ersten Lackschicht, die in Kontakt zu der gebildeten Metallschicht steht, zu einer Änderung der chemischen Struktur der ersten Lackschicht, die dazu führt, dass die vormals Base-lösliche erste Lackschicht zumindest bereichsweise für die Base unlöslich wird und eine Strukturierung der Metallschicht somit erschwert oder verhindert.Such a method and such a transfer sheet are known from WO 98/50241 known. Here is a composite film structure disclosed in some areas Having reflective metal layer which is formed congruent or accurate register on areas of a lacquer layer. In this case, a carrier film is coated with a soluble, optionally colored first lacquer layer and the side of the first lacquer layer facing away from the carrier film is covered with a reflective metal layer. Now, portions of the metal layer are to be removed by either coating a base in a desired pattern on the metal layer, or coating a base-insoluble layer in a pattern on the metal layer, and then coating a base onto the insoluble layer and the exposed areas of the metal layer Metal layer is applied. The base should now dissolve through the metal layer through the soluble first coat of paint. However, it has proved to be extremely difficult to completely solve the first coat of paint in this way reliably and in the desired areas. The reason for this seems to be due to the deposited metal layer which is usually formed by vapor deposition or sputtering on the first lacquer layer typically via a PVD process (P hysical V apour D eposition). At least in the region of the surface of the first lacquer layer, which is in contact with the metal layer formed, there is a change in the chemical structure of the first lacquer layer, which results in the previously base-soluble first lacquer layer becoming insoluble at least in some areas for the base and thus complicates or prevents structuring of the metal layer.

Aus der DE 102 56 491 A1 ist es bekannt, eine Metallschicht partiell mit einem Ätzresistlack zu beschichten und die freiliegenden Bereiche der Metallschicht durch Ätzen zu entfernen, um eine bereichsweise Metallisierung zu erzeugen. Weiterhin ist es offenbart, auf ein Trägersubstrat bereichsweise eine lösliche Lackschicht aufzubringen, eine Metallschicht über der Lackschicht und den davon freien Bereichen des Trägersubstrats anzuordnen und die Lackschicht anschließend zu lösen, um eine bereichsweise Metallisierung des Trägersubstrats zu erzeugen.From the DE 102 56 491 A1 It is known to coat a metal layer partially with an etching resist and to remove the exposed areas of the metal layer by etching to produce a partial metallization. It is further disclosed to apply a soluble lacquer layer in regions to a carrier substrate, to arrange a metal layer over the lacquer layer and the free regions of the carrier substrate and subsequently to dissolve the lacquer layer in order to produce a partial metallization of the carrier substrate.

Außerdem ist hier ein Verfahren beschrieben, bei dem ein löslicher Lack bereichsweise mit einem Härtungsmittel bedruckt wird, das Härtungsmittel und davon freie Bereiche des Lacks mit einer Metallschicht beschichtet werden und anschließend der Lack in den Bereichen, in denen kein Härtungsmittel vorhanden war inklusive der darauf angeordneten Metallschicht zu lösen, um eine bereichsweise Metallisierung des Trägersubstrats passergenau zu den gehärteten Bereichen des Lacks zu erzeugen. Wie bereits oben beschrieben führen diese beiden zuletzt beschriebenen Verfahren bei einer Vielzahl von Lacken dazu, dass die Löslichkeit der Lackschicht nach der Metallisierung deutlich verschlechtert ist, so dass ein definiertes Ablösen der Lackschichtbereiche, die direkt mit der Metallschicht versehen wurden, erschwert oder gar unmöglich ist.In addition, a method is described here in which a soluble paint is partially printed with a curing agent, the curing agent and free areas of the paint are coated with a metal layer and then the paint in the areas where no curing agent was present including the arranged thereon Dissolve metal layer to produce a partial metallization of the carrier substrate registering to the cured areas of the paint. As already described above, these two methods last described in the case of a large number of paints cause the solubility of the lacquer layer after metallization to be markedly worsened, so that a defined detachment of the lacquer layer areas provided directly with the metal layer is made difficult or even impossible ,

Weiterhin ist beschrieben, dass eine lösliche erste Farb- oder Lackschicht vollflächig auf ein Trägersubstrat aufgetragen wird und partiell mit einer zweiten Farb- oder Lackschicht bedeckt wird, die einen Härter für die erste Schicht enthält. Die Bereiche der ersten Schicht, in denen die zweite Schicht nicht vorhanden war, werden durch ein Lösemittel gelöst, so dass Bereiche mit zwei passergenauen Farbschichten gebildet werden.Furthermore, it is described that a soluble first color or lacquer layer is applied over its entire surface to a carrier substrate and is partially covered with a second color or lacquer layer which contains a hardener for the first layer. The areas of the first layer in which the second layer was absent are dissolved by a solvent, so that areas with two register-accurate color layers are formed.

DE 34 30 111 C1 offenbart eine Folie mit einer dekorativen Metallschicht und ein Verfahren zu deren Herstellung. Dabei wird ein löslicher Lack auf einer Trägerfolie bereichsweise mit einem Härtungsmittel oder einem Aushärtlack, der einen Härter im Überschuss enthält, bedruckt. Der Härter diffundiert in den darunter liegenden, löslichen Lack und härtet diesen. Dabei bildet sich ein Konzentrationsgefälle des Härters im löslichen Lack aus, wobei in Richtung der Trägerfolie die Härter-Konzentration abnimmt und dadurch eine örtlich unterschiedlich starke Härtung der löslichen Schicht bewirkt wird. Dadurch können im Bereich der Trägerfolie ungehärtete Bereiche des löslichen Lacks vorliegen, die beim Abwaschen der Bereiche, die nicht mit Härtungsmittel bedruckt wurden, ebenfalls ganz oder teilweise mit abgelöst werden. Aber auch wenn die Härtung des löslichen Lacks im Bereich der Trägerfolie soweit ausreicht, dass eine Löslichkeit nicht mehr gegeben ist, wirkt sich die aufgrund des Konzentrationsgefälles auftretende ungleichmäßige Härtung des löslichen Lacks auf seine mechanischen Eigenschaften ungünstig aus. Weiterhin bleibt immer ein Rest des reinen Härtungsmittels (oder aber der Aushärtlack) an der Oberfläche des vormals löslichen Lacks zurück und befindet sich somit zwischen der Metallschicht und dem vormals löslichen Lack. Dies kann zu einer unzureichenden Haftung der Metallisierung führen. DE 34 30 111 C1 discloses a foil with a decorative metal layer and a method for its production. In this case, a soluble coating on a carrier film is partially printed with a curing agent or a Aushärtlack containing a curing agent in excess. The hardener diffuses into the underlying, soluble paint and hardens it. In this case, a concentration gradient of the hardener is formed in the soluble paint, wherein in the direction of the carrier film, the hardener concentration decreases and thereby a locally different degrees of hardening of the soluble layer is effected. As a result, uncured areas of the soluble lacquer may be present in the region of the carrier film which, during the washing of the Areas that have not been printed with curing agent, also be partially or completely replaced with. But even if the curing of the soluble paint in the region of the support film is sufficient so far that solubility is no longer present, the non-uniform hardening of the soluble paint due to the concentration gradient has an unfavorable effect on its mechanical properties. Furthermore, always a residue of the pure curing agent (or the Aushärtlack) remains on the surface of the previously soluble paint and is thus located between the metal layer and the formerly soluble paint. This can lead to insufficient adhesion of the metallization.

Es ist nun Aufgabe der Erfindung, eine verbessertes Verfahren zur Bildung einer bereichsweisen, passergenauen Metallisierung auf einem Trägersubstrat sowie eine Transferfolie mit scharf abgegrenzten, passergenauen Metallisierungsbereichen bereitzustellen.It is an object of the invention to provide an improved method for forming a zone-wise, registration-accurate metallization on a carrier substrate as well as a transfer film with sharply demarcated, register-accurate metallization regions.

Die Aufgabe wird für das Verfahren, bei welchem das Trägersubstrat zumindest bereichsweise mit einer löslichen, farbigen ersten Schicht versehen wird, die auf ihrer dem Trägersubstrat abgewandten Seite vollflächig mit einer Metallschicht versehen wird, dadurch gelöst, dass entweder

  1. a) zwischen der ersten Schicht und der Metallschicht partiell zumindest eine lösliche zweite Schicht angeordnet wird, oder dass
  2. b) auf der, der Metallschicht zugewandten Seite der ersten Schicht bereichsweise mindestens eine unlösliche dritte Schicht angeordnet wird und dass eine lösliche zweite Schicht zumindest partiell auf die der Metallschicht zugewandte Seite der dritten Schicht sowie partiell auf die von der dritten Schicht freien Bereiche der ersten Schicht aufgetragen wird,
    wobei in den Fällen a) und b)
    • der ersten Schicht ein Härter zugesetzt ist und der zweiten Schicht ein Zusatzstoff zugesetzt ist, der dazu geeignet ist, den Härter der ersten Schicht zu inaktivieren, wobei die gegebenenfalls angeordnete, mindestens eine dritte Schicht für den den Zusatzstoff undurchdringlich ist,
    • der Zusatzstoff der zweiten Schicht den Härter der ersten Schicht in den Bereichen der ersten Schicht, die in direktem Kontakt zur zweiten Schicht angeordnet sind, inaktiviert, bevor die erste Schicht durch den Härter gehärtet wird, und dass
    • die zweite Schicht und die Bereiche der ersten Schicht, in denen der Härter inaktiviert wurde, mittels einer Flüssigkeit gelöst und entfernt werden, wobei die Metallschicht in den Bereichen entfernt wird, die unmittelbar auf der zweiten Schicht angeordnet wurden.
The object is achieved for the method in which the carrier substrate is at least partially provided with a soluble, colored first layer, which is provided on its side facing away from the carrier substrate with a metal layer, achieved either
  1. a) partially at least one soluble second layer is disposed between the first layer and the metal layer, or that
  2. b) on the, the metal layer facing side of the first layer partially at least one insoluble third layer is arranged and that a soluble second layer at least partially on the side facing the metal layer of the third layer and partially on the third layer free areas of the first layer is applied,
    in cases a) and b)
    • a hardener is added to the first layer and an additive is added to the second layer which is suitable for inactivating the hardener of the first layer, the optionally arranged, at least one third layer for which the additive is impermeable,
    • the additive of the second layer inactivates the hardener of the first layer in the regions of the first layer that are disposed in direct contact with the second layer before the first layer is cured by the hardener, and that
    • the second layer and the areas of the first layer in which the hardener has been inactivated are dissolved and removed by means of a liquid, the metal layer being removed in the areas which have been arranged directly on the second layer.

Erfindungsgemäß werden demnach die Bereiche der ersten Schicht, die wieder gelöst werden sollen, an keiner Stelle unmittelbar mit der Metallschicht beschichtet, so dass eine Veränderung der Löslichkeit der ersten Schicht durch die Beschichtung mit der Metallschicht unterbleibt. Die Bereiche der ersten Schicht, die wieder gelöst werden sollen, werden gemäß der Erfindung in direkten Kontakt mit der zweiten Schicht gebracht, die einen Zusatzstoff aufweist, der auf einen in der ersten Schicht enthaltenen Härter abgestimmt ist. Der Zusatzstoff in der zweiten Schicht inaktiviert den Härter in der ersten Schicht, bevor der Härter aktiv wird und die erste Schicht härtet. Die zweite Schicht und davon frei gelassene Bereiche der ersten Schicht werden mit einer Metallschicht, die vorzugsweise in einem PVD-Verfahren wie dem Aufdampfen oder der Kathodenzerstäubung gebildet wird, beschichtet. Nach einer lediglich bereichsweisen Härtung der ersten Schicht in den Bereichen der ersten Schicht, die nicht mit der zweiten Schicht beschichtet wurden und in denen daher eine Inaktivierung des Härters in der ersten Schicht nicht erfolgt ist, wird die zweite Schicht und die Bereiche der ersten Schicht, in denen der Härter inaktiviert wurde, mittels der Flüssigkeit gelöst und entfernt. Dabei wird auch der Teil der Metallschicht entfernt, der unmittelbar auf der zweiten Schicht angeordnet ist und es wird somit eine bereichsweise Metallisierung auf dem Trägersubstrat gebildet. Die bereichsweise Metallisierung befindet sich an den Stellen, an denen die erste Schicht direkt mit der Metallschicht beschichtet und gehärtet wurde. Die in Fall b) vorhandene, mindestens eine dritte Schicht ist unlöslich und ermöglicht zusätzliche dekorative Effekte. Dabei können sich die optischen Eindrücke der ersten und der dritten Schicht überlagern und auch die dritte Schicht zumindest bereichsweise mit der Metallschicht versehen werden. Das erfindungsgemäße Verfahren ermöglicht eine zuverlässige Ablösung der ungehärteten Bereiche der ersten Schicht und der darauf angeordneten Bereiche der Metallschicht, wobei reproduzierbar Metallschichtbereiche mit definierten Abmessungen und scharfen Rändern erzeugt werden können. Einerseits wird die erste Lackschicht in gehärtete und ungehärtete Bereiche aufgeteilt und andererseits werden die zu härtenden Bereiche der ersten Lackschicht zudem direkt mit der Metallschicht beschichtet, was zu der oben beschriebenen Verminderung der Löslichkeit der ersten Lackschicht führt. Diese doppelte Einflussnahme auf die erste Lackschicht ist als Ursache für die hohe Randschärfe der gebildeten Metallisierungsbereiche und für die extrem hohe Passergenauigkeit der gehärteten Bereiche der ersten Lackschicht und der darauf angeordneten Bereiche der Metallschicht zu sehen.According to the invention, therefore, the regions of the first layer which are to be dissolved again are not coated directly with the metal layer at any point, so that there is no change in the solubility of the first layer due to the coating with the metal layer. The regions of the first layer which are to be redissolved are, according to the invention, brought into direct contact with the second layer, which has an additive which is adapted to a hardener contained in the first layer. The additive in the second layer inactivates the hardener in the first layer before the hardener becomes active and hardens the first layer. The second layer and exposed portions of the first layer are coated with a metal layer, which is preferably formed in a PVD process such as vapor deposition or sputtering. After an only partial hardening of the first layer in the regions of the first layer which were not coated with the second layer and in which therefore inactivation of the hardener in the first layer has not occurred, the second layer and the regions of the first layer, in which the hardener was inactivated, dissolved by means of the liquid and removed. It also becomes the part of the metal layer removed, which is arranged directly on the second layer, and thus a partial metallization is formed on the carrier substrate. The partial metallization is located where the first layer was directly coated and cured with the metal layer. The at least one third layer present in case b) is insoluble and allows additional decorative effects. In this case, the optical impressions of the first and the third layer can overlap and also the third layer can be provided at least in regions with the metal layer. The method according to the invention enables a reliable detachment of the uncured regions of the first layer and the regions of the metal layer arranged thereon, it being possible to reproducibly produce metal layer regions having defined dimensions and sharp edges. On the one hand, the first lacquer layer is divided into hardened and uncured regions, and on the other hand, the regions of the first lacquer layer to be hardened are additionally directly coated with the metal layer, which leads to the above-described reduction of the solubility of the first lacquer layer. This double influence on the first lacquer layer can be seen as the cause for the high edge sharpness of the formed metallization areas and for the extremely high registration accuracy of the hardened areas of the first lacquer layer and the areas of the metal layer arranged thereon.

Besonders vorteilhaft ist dabei im Vergleich zur DE 34 30 111 C1 , dass die erfindungsgemäß unter den Bereichen der Metallschicht verbleibenden, gehärteten Bereiche der ersten Schicht aufgrund ihrer Herstellungsgeschichte einen gleichmäßigen Härtungsgrad über ihre Fläche als auch - im Querschnitt gesehen - über ihre Schichtdicke aufweisen, da der Härter bereits bei der Bildung der ersten Schicht gleichmäßig im Material zur Bildung der ersten Schicht verteilt ist. Die gleichmäßige Härtung der ersten Schicht kann beispielsweise dadurch festgestellt werden, dass der Abrieb, die Löslichkeit, der Brechungsindex, die Molmasse oder ein Molekulargewicht der ersten Schicht - im Querschnitt gesehen - für unterschiedliche Schichttiefen ermittelt und miteinander verglichen wird. Weiterhin ist es möglich, den Härtungsgrad der ersten Schicht beispielsweise über den Dampfdruck von Polymeren in der ersten Schicht oder durch eine Ermittlung der Verformbarkeit der ersten Schicht - ebenfalls im Querschnitt gesehen - für unterschiedliche Schichttiefen zu ermitteln und miteinander zu vergleichen. Bei dem erfindungsgemäßen verfahren sind in der resultierenden, gehärteten ersten Schicht keine unterschiedlichen Messwerte festzustellen.It is particularly advantageous compared to DE 34 30 111 C1 in that, according to the invention, the hardened regions of the first layer remaining under the regions of the metal layer have a uniform degree of cure over their surface and, seen in cross-section, over their layer thickness, since the hardener is uniform in the material even in the formation of the first layer is distributed to form the first layer. The uniform hardening of the first layer can be determined, for example, by the fact that the abrasion, the solubility, the refractive index, the molecular weight or a Molecular weight of the first layer - seen in cross-section - determined for different layer depths and compared. Furthermore, it is possible to determine the degree of hardening of the first layer, for example via the vapor pressure of polymers in the first layer or by determining the deformability of the first layer - also seen in cross section - for different layer depths and to compare them. In the method according to the invention, no different measured values can be ascertained in the resulting, hardened first layer.

Insbesondere hat es sich für das Verfahren bewährt, wenn ein Härter in der ersten Schicht auf Aziridin-Basis oder auf Polyimin-Basis gewählt wird und die zweite Schicht aus einer wasserlöslichen, stark alkalischen Druckfarbe mit einem pH-Wert im Bereich von 11 bis 14 gebildet wird.In particular, it has proven useful for the process when a hardener in the first aziridine-based or polyimine-based layer is selected and the second layer is formed from a water-soluble, highly alkaline ink having a pH in the range of 11 to 14 becomes.

Insbesondere hat es sich dabei bewährt, wenn die Druckfarbe mittels Natriumhydroxid oder Kaliumhydroxid alkalisch ausgebildet wird, wobei das Natriumhydroxid beziehungsweise das Kaliumhydroxid den Zusatzstoff bildet. Es hat sich erwiesen, dass diese Zusatzstoffe aus der zweiten Schicht einen Härter auf Aziridin-Basis oder Polyimin-Basis in der ersten Schicht zuverlässig inaktivieren und somit die Härtung der ersten Schicht reproduzierbar bereichsweise verhindern. Derartige Härter härten die erste Schicht erst bei Temperaturen oberhalb ca. 80°C beschleunigt aus. Bei Raumtemperatur verläuft die Härtung nur sehr langsam, so dass eine Inaktivierung des Härters durch den Zusatzstoff in der Druckfarbe erfolgen kann, insbesondere, wenn diese "inline" in einem nachfolgenden Druckwerk auf der ersten Schicht aufgebracht wird.In particular, it has proven to be useful if the ink is formed alkaline by means of sodium hydroxide or potassium hydroxide, wherein the sodium hydroxide or potassium hydroxide forms the additive. It has been found that these additives from the second layer reliably inactivate an aziridine-based or polyimine-based hardener in the first layer and thus prevent the hardening of the first layer in a reproducible area. Such hardeners cure the first layer only at temperatures above about 80 ° C accelerated. At room temperature, the curing is very slow, so that inactivation of the curing agent by the additive in the ink can be done, especially if this is applied "inline" in a subsequent printing on the first layer.

Die Druckfarbe zur Bildung der zweiten Schicht wird dabei vorzugsweise mit einem färbenden Füllstoff oder Pigment versetzt wird, um die Anordnung und Ausbildung der gebildeten zweiten Schicht in einfacher Weise einer optischen Kontrolle unterziehen zu können. Dabei hat es sich bewährt, der Druckfarbe Bariumsulfat, Titanoxid oder Zinksulfid zuzusetzen, um diese gut sichtbar zu machen.The printing ink for forming the second layer is preferably added with a coloring filler or pigment to the arrangement and training the formed second layer in a simple manner to undergo a visual inspection. It has proven useful to add barium sulfate, titanium oxide or zinc sulfide to the ink in order to make them visible.

Die Aufgabe wird für die Transferfolie, insbesondere eine Heißprägefolie, dadurch gelöst, dass die erste Schicht mittels eines Härters auf Aziridin-Basis oder auf Polyimin-Basis gehärtet ist, wobei die erste Schicht über deren Schichtdicke gesehen gleichmäßig ausgehärtet ist.The object is achieved for the transfer film, in particular a hot stamping foil, by hardening the first layer by means of an aziridine-based or polyimine-based hardener, the first layer having cured uniformly over its layer thickness.

Es resultieren optimale mechanische Eigenschaften der ersten Schicht verbunden mit einer guten Haftung der Metallschicht auf der gehärteten ersten Schicht.This results in optimum mechanical properties of the first layer combined with good adhesion of the metal layer on the cured first layer.

Aufgrund der örtlich scharf begrenzten Einflusswirkung einer Base auf einen solchen Härter im direkten Kontaktbereich sind scharf abgegrenzte Bereiche der ersten Schicht erzeugbar und somit passergenau auch scharf abgegrenzte Metallisierungsbereiche vorhanden.Due to the locally sharply limited influence of a base on such a curing agent in the direct contact area sharply demarcated areas of the first layer can be generated and thus accurately defined even sharply demarcated metallization areas available.

Die erste Schicht wird vorzugsweise durch einen alkalilöslichen Lack, vorzugsweise auf Basis von Polyacrylsäure oder Styrol-Maleinsäureanhydrid, gebildet.The first layer is preferably formed by an alkali-soluble lacquer, preferably based on polyacrylic acid or styrene-maleic anhydride.

Für die erste Schicht wird bevorzugt eine Schichtdicke im Bereich von 0,7 bis 2 µm gewählt. In diesem Bereich kann der Zusatzstoff der zweiten Schicht den Härter in der ersten Schicht über die gesamte Schichtdicke der ersten Schicht hinweg zuverlässig inaktivieren. Es hat sich bewährt, die zweite Schicht mit einer Dicke im Bereich von 0,8 bis 3 µm auszubilden.For the first layer, a layer thickness in the range of 0.7 to 2 μm is preferably selected. In this area, the additive of the second layer can reliably inactivate the hardener in the first layer over the entire layer thickness of the first layer. It has proven useful to form the second layer with a thickness in the range of 0.8 to 3 microns.

Es hat sich bewährt, wenn die erste Schicht transparent ist, um den Metallspiegel durch die erste Schicht hindurch sichtbar zu machen und voll zur Geltung zu bringen. Die erste Schicht kann sich dabei aus mehreren transparenten Schichten zusammensetzen, deren optische Wirkung sich gegenseitig beeinflusst.It has proved useful if the first layer is transparent in order to make visible and fully emphasize the metal mirror through the first layer. The first layer may consist of several transparent layers whose optical effect influences each other.

Es hat sich bewährt, wenn die Trägerfolie und/oder die Übertragungslage der Transferfolie zumindest teilweise transparent sind. Beispielsweise ermöglichen bereichsweise transparente Übertragungslagen, die auf einem Wertdokument aufgebracht werden, die Oberfläche des Wertdokumentes noch zu erkennen und eine zusätzliche Fälschungssicherheit zu erreichen.It has proven useful if the carrier film and / or the transfer layer of the transfer film are at least partially transparent. For example, partially transparent transfer layers, which are applied to a document of value, still allow the surface of the document of value to be recognized and to achieve additional protection against counterfeiting.

Es hat sich bewährt, wenn die Übertragungslage eine Kleberschicht aufweist, wobei die Kleberschicht an der, der Trägerfolie abgewandten Seite der Übertragungslage angeordnet ist. Bei Verwendung eines transparenten Klebers für die Kleberschicht zum Aufkaschieren der Übertragungslage auf ein transparentes Substrat bleiben durch das Substrat und die Kleberschicht hindurch farbige Schichten und Metallschichten der Übertragungslage erkennbar.It has proven useful if the transfer layer has an adhesive layer, wherein the adhesive layer is arranged on the side of the transfer layer facing away from the carrier film. When using a transparent adhesive for the adhesive layer for laminating the transfer layer to a transparent substrate, colored layers and metal layers of the transfer layer remain visible through the substrate and the adhesive layer.

Mit der mindestens einen dritten Schicht, die in der Übertragungslage vorgesehen sein kann, lassen sich besondere dekorative Effekte erzielen, wenn diese farbig opak und/oder farbig transparent ausgebildet wird.With the at least one third layer, which may be provided in the transfer layer, it is possible to achieve special decorative effects if this is made opaque in color and / or colored transparent.

Um eine Übertragung der Übertragungslage der Transferfolie auf beispielsweise ein Wertdokument zu erleichtern, hat es sich als vorteilhaft erwiesen, wenn zwischen der Trägerfolie und der Übertragungslage eine wachsartige Trennschicht angeordnet ist. Derartige Trennschichten weisen üblicherweise eine Dicke im Bereich von 0,001 bis 0,1 µm auf. Die Trägerfolie, die vorzugsweise aus Kunststoffen wie beispielsweise PI, PP, PE, PET, PPS, LCP, PEN, PA, PVC, aus Papier, Geweben oder Metallfolie gebildet ist, löst sich dadurch unter Druck und Temperatur beim Heißprägen leicht von der Übertragungslage und ermöglicht eine genaue und vollständige Applikation auf ein zu beprägendes Material.In order to facilitate a transfer of the transfer layer of the transfer film to, for example, a document of value, it has proved to be advantageous if a wax-like separating layer is arranged between the carrier film and the transfer layer. Such separating layers usually have a thickness in the range of 0.001 to 0.1 μm. The carrier film, preferably made of plastics such as PI, PP, PE, PET, PPS, LCP, PEN, PA, PVC, paper, fabrics or metal foil, thereby dissolves easily under pressure and temperature during hot stamping of the transfer layer and allows accurate and complete application to a material to be embossed.

Besonders bevorzugt ist es, als Trägersubstrat ein flexibles Folienmaterial mit einer Dicke im Bereich von 5 bis 700 µm, vorzugsweise im Bereich von 12 bis 50 µm, einzusetzen, so das dieses auf einer Vorratsrolle bereitgestellt und endlos verarbeitet werden kann.
Besonders vorteilhaft ist es dabei, wenn das Trägersubstrat zur Ausbildung der bereichsweisen Metallisierung von Rolle zu Rolle transportiert wird. Das bedeutet, dass das Trägersubstrat von einer ersten Vorratsrolle abgezogen, dem erfindungsgemäßen Verfahren, gegebenenfalls auch weiteren Verfahrensschritten unterzogen, und schließlich auf eine zweite Vorratsrolle aufgewickelt werden kann, die weiterverarbeitet wird. Als weitere Verfahrensschritte kommen beispielsweise Prägevorgänge, Temperaturbehandlungen oder auch eine Bestrahlung in Betracht.It is particularly preferred to use a flexible film material having a thickness in the range from 5 to 700 .mu.m, preferably in the range from 12 to 50 .mu.m, as the carrier substrate, so that this can be provided on a supply roll and processed endlessly.
It is particularly advantageous in this case if the carrier substrate is transported from roll to roll to form the zone-wise metallization. This means that the carrier substrate withdrawn from a first supply roll, the process of the invention, optionally also subjected to further process steps, and finally can be wound onto a second supply roll, which is further processed. Further process steps include, for example, embossing processes, temperature treatments or irradiation.

Weiterhin ist es besonders bevorzugt, wenn die Metallschicht reflektierend, vorzugsweise spiegelnd reflektierend ausgebildet wird. Dadurch wird der dekorative Effekt der bereichsweisen Metallisierung noch erhöht.Furthermore, it is particularly preferred if the metal layer is designed to be reflective, preferably reflective and reflective. This further enhances the decorative effect of the area-wise metallization.

Es hat sich bewährt, wenn die Metallschicht aus einem der Metalle Aluminium, Chrom, Kupfer, Nickel, Eisen, Titan, Silber, Gold oder einer Legierung aus zwei oder mehreren dieser Metalle gebildet wird. Diese Metalle können eine spiegelnd reflektierende Metallschichten erzeugen.It has proven useful if the metal layer is formed from one of the metals aluminum, chromium, copper, nickel, iron, titanium, silver, gold or an alloy of two or more of these metals. These metals can produce a specularly reflective metal layer.

Die Metallschicht wird bevorzugt durch Aufdampfen oder Kathodenzerstäubung gebildet, da diese Verfahren in einem kontinuierlichen und damit besonders wirtschaftlichen Prozess erfolgen können.The metal layer is preferably formed by vapor deposition or cathode sputtering, since these methods can be carried out in a continuous and thus particularly economical process.

Es ist bevorzugt, die Metallschicht(en) in einer Dicke im Bereich von 10 bis 100 nm auszubilden.It is preferable to form the metal layer (s) in a thickness in the range of 10 to 100 nm.

Die Verwendung der erfindungsgemäßen Transferfolie zur Bildung von Sicherheitselementen auf Datenträgern, insbesondere Wertdokumenten wie Ausweisen, Karten oder Banknoten, von Bauelementen oder dekorativen Elementen, insbesondere in der Architektur oder anderen technischen Bereichen, von Verpackungsmaterialien, insbesondere in der pharmazeutischen oder Lebensmittelindustrie oder von Bauteilen in der Elektro- oder Elektronikindustrie ist ideal.The use of the transfer film according to the invention for the formation of security elements on data carriers, in particular value documents such as identity cards, cards or banknotes, of components or decorative elements, in particular in architecture or other technical fields, of packaging materials, in particular in the pharmaceutical or food industry or of components in the Electrical or electronics industry is ideal.

Die Figuren 1a bis 3 sollen das erfindungsgemäße Verfahren und den Aufbau einer erfindungsgemäßen Transferfolie beispielhaft erläutern. So zeigt:

Figur 1a
ein Trägersubstrat mit einer ersten Schicht, einer zweiten Schicht und einer Metallschicht im Querschnitt,
Figur 1b
das Trägersubstrat aus Figur 1a nach dem Lösen der zweiten Schicht und nicht gehärteter Bereiche der ersten Schicht,
Figur 2a
ein weiteres Trägersubstrat mit einer ersten Schicht, einer zweiten Schicht, einer dritten Schicht und einer Metallschicht im Querschnitt,
Figur 2b
das Trägersubstrat aus Figur 2a nach dem Lösen der zweiten Schicht und nicht gehärteter Bereiche der ersten Schicht, und
Figur 3
den Querschnitt durch eine als Heißprägefolie ausgebildete Transferfolie mit bereichsweiser Metallisierung.
The FIGS. 1a to 3 The process according to the invention and the structure of a transfer film according to the invention are intended to illustrate by way of example. So shows:
FIG. 1a
a carrier substrate having a first layer, a second layer and a metal layer in cross-section,
FIG. 1b
the carrier substrate FIG. 1a after dissolving the second layer and uncured areas of the first layer,
FIG. 2a
a further carrier substrate having a first layer, a second layer, a third layer and a metal layer in cross section,
FIG. 2b
the carrier substrate FIG. 2a after dissolving the second layer and uncured areas of the first layer, and
FIG. 3
the cross section through a trained as a hot stamping foil transfer film with areawise metallization.

Figur 1a zeigt im Querschnitt ein als Trägerfolie ausgebildetes Trägersubstrat 1, das mit einem alkalilöslichen, farbigen Lack auf Basis von Styrol-Maleinsäureanhydrid (SMA) als erste Schicht 2 beschichtet ist. FIG. 1a shows in cross-section as a support film formed carrier substrate 1, which is coated with an alkali-soluble, colored paint based on styrene-maleic anhydride (SMA) as a first layer 2.

Der Lack zur Bildung der ersten Schicht wies folgende Zusammensetzung auf: Ethanol 3200g Ethylacetat 3100g n-Butanol 100g SMA-Harz (MW ca. 200000, Säurezahl ca. 250) 1000g Alkohollösliches Cellulosenitrat (Norm 30 A) 100g Komplexfarbstoff Orange 85g Komplexfarbstoff Gelb 38g Aziridin-Härter 25g The lacquer for forming the first layer had the following composition: ethanol 3200g ethyl acetate 3100g n-butanol 100 g SMA resin (MW approx. 200000, acid number approx. 250) 1000g Alcohol-soluble cellulose nitrate (standard 30 A) 100 g Complex dye orange 85g Complex dye yellow 38g Aziridine hardener 25g

Das Trägersubstrat 1 aus PET weist dabei eine Dicke von 25µm auf und die erste Schicht 2 weist eine Dicke von 1µm auf. Die erste Schicht 2 kann dabei vollflächig oder nur partiell auf dem Trägersubstrat 1 aufgetragen sein. Die erste Schicht 2 enthält im vorliegenden Fall einen Härter auf Aziridin-Basis. Zwischen dem Trägersubstrat 1 und der ersten Schicht 2 können weitere Lackschichten, reflektierende Schichten oder sonstige Schichten angeordnet sein, die beispielsweise magnetische Eigenschaften aufweisen können. Auf der ersten Schicht 2 ist partiell eine wasserlösliche, stark alkalische Druckfarbe als zweite Schicht 3 aufgebracht, die als Zusatzstoff Natriumhydroxid enthält und eine Dicke von 1,5 µm aufweist. Der Druckfarbe wurde Titanoxid zugesetzt, um ein gut sichtbares und kontrollierbares Druckergebnis zu erhalten.The carrier substrate 1 made of PET has a thickness of 25 .mu.m and the first layer 2 has a thickness of 1 .mu.m. The first layer 2 can be applied over the entire surface or only partially on the carrier substrate 1. The first layer 2 in the present case contains an aziridine-based hardener. Between the carrier substrate 1 and the first layer 2 further lacquer layers, reflective layers or other layers can be arranged, which may have, for example, magnetic properties. On the first layer 2 is partially applied a water-soluble, strongly alkaline printing ink as a second layer 3, which contains sodium hydroxide as an additive and has a thickness of 1.5 microns. The ink was added to titanium oxide to give a highly visible and controllable print result.

Die Druckfarbe zur Bildung der zweiten Schicht wies folgende Zusammensetzung auf: Wasser 9200g Methylcellulose (niedermolekular) 750g Silika hochdispers 150g Titandioxid (Rutiltype) 2000g Ethanol 1000g n-Butanol 600g Natronlauge (50 proz.) 2000g The printing ink for forming the second layer had the following composition: water 9200G Methylcellulose (low molecular weight) 750g Silica fumed 150g Titanium dioxide (rutile type) 2000g ethanol 1000g n-butanol 600g Caustic soda (50 percent) 2000g

Eine spiegelnd reflektierende Metallschicht 4 aus Aluminium, welche eine Dicke von 40nm aufweist, bedeckt die zweite Schicht 3 sowie die davon unbedeckten Bereiche der ersten Schicht 2. Das Natriumhydroxid der zweiten Schicht 3 inaktiviert den Härter in der ersten Schicht 2 in den Bereichen, in denen ein direkter Kontakt zwischen der ersten Schicht 2 und der zweiten Schicht 3 erzeugt wurde.A specularly reflective metal layer 4 of aluminum having a thickness of 40 nm covers the second layer 3 and the uncovered areas of the first layer 2. The sodium hydroxide of the second layer 3 inactivates the hardener in the first layer 2 in the areas in which a direct contact between the first layer 2 and the second layer 3 was generated.

Figur 1b zeigt das Trägersubstrat 1 aus Figur 1a nach dem Lösen der zweiten Schicht 3 und nicht gehärteter Bereiche der ersten Schicht 2 in Wasser. Lediglich in den Bereichen der ersten Schicht 2, die nicht von der zweiten Schicht 3 bedeckt waren, wurde der Härter aktiv und führte zu einer Härtung der ersten Schicht 2. Diese Bereiche verbleiben demnach auf den Trägersubstrat 1 inklusive der sich direkt darauf befindenden, passergenauen Bereiche der Metallschicht 4, während die ungehärteten Bereiche der ersten Schicht 2 und die auf der zweiten Schicht 3 angeordneten Bereiche der Metallschicht 4 entfernt wurden.
Figur 2a zeigt ein weiteres Trägersubstrat 1 mit einer darauf vollflächig aufgebrachten, wasserlöslichen ersten Schicht 2 auf Basis von Styrol-Maleinsäureanhydrid gemäß Figur 1a, die einen Härter auf Aziridin-Basis enthält. Die erste Schicht 2 ist farbig und transparent. Auf der ersten Schicht 2 ist partiell eine wasserunlösliche, farbig transparente dritte Schicht 7 aufgebracht. FIG. 1b shows the carrier substrate 1 from FIG. 1a after dissolving the second layer 3 and uncured areas of the first layer 2 in water. Only in the areas of the first layer 2, which were not covered by the second layer 3, the curing agent became active and led to a hardening of the first layer 2. These areas thus remain on the carrier substrate 1, including the registration areas located directly on it of the metal layer 4, while the uncured portions of the first layer 2 and the portions of the metal layer 4 disposed on the second layer 3 have been removed.
FIG. 2a shows a further carrier substrate 1 with a completely applied thereto, water-soluble first layer 2 based on styrene-maleic anhydride according to FIG. 1a containing an aziridine-based hardener. The first layer 2 is colored and transparent. On the first layer 2, a water-insoluble, color-transparent third layer 7 is partially applied.

Der wasserunlösliche Lack zur Bildung der dritten Schicht wies folgende Zusammensetzung auf: Methylethylketon 2600g PMMA (hochmolekular, Tg 120°C) 500g Toluol 2000g Esterlösliches Cellulosenitrat (Norm 34 E) 1000g Cyclohexanon 300g Komplexfarbstoff Rot 45g The water-insoluble varnish for forming the third layer had the following Composition on: methyl ethyl ketone 2600g PMMA (high molecular weight, Tg 120 ° C) 500g toluene 2000g Ester-soluble cellulose nitrate (standard 34 E) 1000g cyclohexanone 300g Complex dye red 45g

Dabei ist partiell auf der dritten Schicht 7 und partiell auf den von der dritten Schicht 7 unbedeckten Bereichen der ersten Schicht 2 eine wasserlösliche, zweite Schicht 3 angeordnet, die aus einer stark alkalischen Druckfarbe gemäß Figur 1a gebildet. Die zweite Schicht 3 enthält als Zusatzstoff Natriumhydroxid, das den Härter in der ersten Schicht 2 in den Bereichen inaktiviert, die damit in direktem Kontakt stehen. Auf die dritte Schicht 7 wirkt sich die zweite Schicht 3 jedoch nicht aus, so dass die dritte Schicht 7 für das Natriumhydroxid der zweiten Schicht 3 eine Sperrschicht bildet. Eine geschlossene Metallschicht 4 aus Chrom bedeckt die zweite Schicht 3, Teile der ersten Schicht 2 sowie Teile der dritten Schicht 7.In this case, partially on the third layer 7 and partially on the uncovered from the third layer 7 areas of the first layer 2, a water-soluble, second layer 3 is arranged, which consists of a strong alkaline ink according to FIG. 1a educated. The second layer 3 contains as additive sodium hydroxide which inactivates the hardener in the first layer 2 in the areas which are in direct contact therewith. However, the second layer 3 does not affect the third layer 7, so that the third layer 7 for the sodium hydroxide of the second layer 3 forms a barrier layer. A closed metal layer 4 of chromium covers the second layer 3, parts of the first layer 2 and parts of the third layer 7.

Figur 2b zeigt das Trägersubstrat 1 aus Figur 2a nach dem Lösen der zweiten Schicht 3 und nicht gehärteter Bereiche der ersten Schicht 2 in Wasser. Auf dem Trägersubstrat 1 verbleiben Bereiche der ersten Schicht 2 passergenau zu Bereichen der Metallschicht 4, unbeschichtete Bereiche der dritten Schicht 7 sowie mit Bereichen der Metallschicht 4 belegte Bereiche der dritten Schicht 7. Durch Variation der Anordnung der einzelnen Schichten lassen sich hier unterschiedlichste Effekte erzielen. FIG. 2b shows the carrier substrate 1 from FIG. 2a after dissolving the second layer 3 and uncured areas of the first layer 2 in water. On the carrier substrate 1, areas of the first layer 2 remain in register with areas of the metal layer 4, uncoated areas of the third layer 7 and areas of the metal layer 4 occupied areas of the third layer 7 Variation of the arrangement of the individual layers can be achieved here very different effects.

Figur 3 zeigt den Querschnitt durch eine Heißprägefolie 10 mit bereichsweiser Metallisierung. Auf einem als Trägerfolie ausgebildeten Trägersubstrat 1 ist eine wachsartige Trennschicht 5 angeordnet, die das Ablösen einer Übertragungslage 9 vom Trägersubstrat 1 auf ein zu beprägendes Material erleichtert. Auf der Trennschicht 5 ist eine farblos transparente, unlösliche Lackschicht 8 angeordnet, auf der Bereiche der ersten Schicht 2 und der Metallschicht 4 wie gemäß Figur 1 b gebildet, angeordnet sind. Eine Kleberschicht 6 befindet sich auf der dem Trägersubstrat 1 abgewandten Seite der Übertragungslage 9. Als Kleber wird vorzugsweise ein heißsiegelfähiger Kleber verwendet. Beim Heißprägen wird die Heißprägefolie 10 unter Temperatureinwirkung mit der Kleberschicht 6 gegen das zu beprägende Material gedrückt und die Übertragungslage 9 ganz oder bereichsweise, beispielsweise in Form von Mustern, alphanumerischen Zeichen oder Bildern, übertragen. Das Trägersubstrat 1 wird von den auf das beprägte Material übertragenen Bereichen der Übertragungslage 9 getrennt. Die farblos transparente Lackschicht 8 bildet nun die Oberfläche der übertragenen Bereiche der Übertragungslage 9 und schützt die darunter angeordneten Schichtlagen, beispielsweise vor Beschädigung oder manipulativer Veränderung. FIG. 3 shows the cross section through a hot stamping foil 10 with areawise metallization. A wax-like separating layer 5, which facilitates the detachment of a transfer layer 9 from the carrier substrate 1 to a material to be embossed, is arranged on a carrier substrate 1 designed as a carrier film. On the release layer 5, a colorless transparent, insoluble resist layer 8 is arranged, on the regions of the first layer 2 and the metal layer 4 as shown in FIG FIG. 1 b formed, are arranged. An adhesive layer 6 is located on the side facing away from the carrier substrate 1 side of the transfer layer 9. As an adhesive, a heat-sealable adhesive is preferably used. When hot stamping the hot stamping film 10 is pressed under the action of temperature with the adhesive layer 6 against the material to be embossed and the transfer layer 9 completely or partially, for example in the form of patterns, alphanumeric characters or images transferred. The carrier substrate 1 is separated from the transferred to the embossed material areas of the transfer layer 9. The colorless transparent lacquer layer 8 now forms the surface of the transferred regions of the transfer layer 9 and protects the layer layers arranged underneath, for example against damage or manipulative change.

Die in den Figuren dargestellten Schichtsysteme sind durch weitere transparente oder opake Schichten ergänzbar, wobei diverse Effekte erzeugt werden können. Auch ein mehrmaliges Anwenden des erfindungsgemäßen Verfahrens in Folge auf einer Trägerfolie, wobei gezielt Sperrschichten zur Verhinderung eines Wirksamwerdens eines Zusatzstoffe in bestimmten Bereichen oder Schichtebenen eingesetzt werden können, ist möglich. Weiterhin kann die erste Schicht 2 aus zwei oder mehr farbigen, transparenten löslichen Lackschichten gebildet sein. Auch können opake Farbschichten zur Strukturierung oder eine Metallschicht eingesetzt werden, die bereichsweise aus Metallen mit unterschiedlicher Farbe gebildet ist.The layer systems shown in the figures can be supplemented by further transparent or opaque layers, whereby various effects can be produced. A repeated application of the method according to the invention in a row on a carrier film, wherein specifically barrier layers can be used to prevent the effectiveness of an additive in certain areas or layer planes, is possible. Furthermore, the first layer 2 can be formed from two or more colored, transparent soluble lacquer layers. Also it is possible to use opaque color layers for structuring or a metal layer which is formed in regions from metals of different colors.

Claims (25)

  1. Process for producing a regional metallization on a carrier substrate (1) wherein the carrier substrate (1) is at least regionally provided with a soluble coloured first layer (2) which on its side remote from the carrier substrate (1) is entirely provided with a metal layer (4),
    characterized in that
    a) at least one soluble second layer (3) is partially arranged between the first layer (2) and the metal layer (4), or in that
    b) regionally at least one insoluble third layer (7) is arranged on that side of the first layer (2) which faces the metal layer (4), and in that a soluble second layer (3) is applied at least partially on to that side of the third layer (7) which faces the metal layer (4) and also partially on to the regions of the first layer (2) which are free of the third layer (7),
    wherein in the cases a) and b)
    - the first layer (2) incorporates a curative, the curative being uniformly distributed in the material for forming the first layer even in the course of the formation of the first layer, and the second layer (3) incorporates an additive capable of inactivating the curative of the first layer (2), wherein the at least one third layer (7) arranged in case b) is impenetrable to the additive,
    - the additive of the second layer (3) inactivates the curative of the first layer (2) in the regions of the first layer (2) which are arranged in direct contact with the second layer (3) before the first layer (2) is cured by the curative, and in that
    - the second layer (3) and the regions of the first layer (2) in which the curative was inactivated are by means of at least one liquid dissolved and removed, wherein the metal layer (4) is removed in the regions which were directly arranged on the second layer (3).
  2. Process according to Claim 1, characterized in that the first layer (2) is formed by an alkali-soluble lacquer, preferably based on polyacrylic acid or styrene-maleic anhydride.
  3. Process according to Claim 2, characterized in that the alkali-soluble lacquer has a water-soluble dye added to it.
  4. Process according to any one of Claims 1 to 3, characterized in that the curative selected is aziridine based or polyimine based and in that the second layer (3) is formed from a water-soluble alkaline printing ink having a pH in the range from 11 to 14.
  5. Process according to Claim 4, characterized in that the printing ink is made alkaline by means of sodium hydroxide or potassium hydroxide as additive.
  6. Process according to either of Claims 4 and 5, characterized in that the printing ink is admixed with a colouring filler or pigment.
  7. Process according to Claim 6, characterized in that the printing ink has barium sulphate, titanium oxide or zinc sulphide added to it.
  8. Process according to any one of Claims 1 to 7, characterized in that the at least one third layer (7) is rendered coloured and opaque and/or coloured and transparent.
  9. Process according to any one of Claims 1 to 8, characterized in that the at least one liquid contains water or consists of water.
  10. Process according to any one of Claims 1 to 9, characterized in that a flexible foil material is used as carrier substrate (1).
  11. Process according to Claim 10, characterized in that the carrier substrate (1) is transported from roll to roll to form the regional metallization.
  12. Process according to any one of Claims 1 to 11, characterized in that the metal layer (4) is reflective, preferably specularly reflective.
  13. Process according to any one of Claims 1 to 12, characterized in that the metal layer (4) is formed from one of the metals aluminium, chromium, copper, nickel, iron, titanium, silver, gold or from an alloy of two or more of these metals.
  14. Process according to any one of Claims 1 to 13, characterized in that the metal layer (4) is formed by vacuum deposition or cathode sputtering.
  15. Transfer foil, more particularly hot-stamping foil, comprising a carrier substrate (1) and a transfer lamina (11) with a regional metallization, obtainable by a process according to any one of Claims 1 to 14, wherein the carrier substrate (1) is formed as a carrier foil and the transfer lamina (11) includes at least one regionally arranged coloured first layer (2) and a metal layer (4), arranged congruently to the first layer (2), as regional metallization,
    characterized in that
    the first layer (2) is cured by means of an aziridine-based or polyimine-based curative incorporated in the first layer, wherein the first layer (2) is uniformly cured throughout its layer thickness, wherein the cured regions of the first layer which remain underneath the regions of the metal layer have a uniform degree of curing throughout their area as well as throughout their layer thickness.
  16. Transfer foil according to Claim 15, characterized in that the first layer (2) is formed by an alkali-soluble lacquer, preferably based on polyacrylic acid or styrene-maleic anhydride.
  17. Transfer foil according to Claim 16, characterized in that the alkali-soluble lacquer contains a water-soluble dye.
  18. Transfer foil according to any one of Claims 15 to 17, characterized in that the metal layer (4) is formed from one of the metals aluminium, chromium, copper, nickel, iron, titanium, silver, gold or from an alloy of two or more of these metals.
  19. Transfer foil according to any one of Claims 16 to 18, characterized in that the metal layer (4) is reflective, preferably specularly reflective.
  20. Transfer foil according to any one of Claims 15 to 19, characterized in that the first layer (2) is formed from one or more transparent layers.
  21. Transfer foil according to any one of Claims 15 to 20, characterized in that the carrier foil and/or the transfer lamellar (11) are at least partly transparent.
  22. Transfer foil according to any one of Claims 15 to 21, characterized in that the transfer lamellar (11) comprises at least one coloured opaque or coloured transparent third layer (7).
  23. Transfer foil according to any one of Claims 15 to 22, characterized in that a wax-like release layer (5) is arranged between the carrier foil and the transfer lamina (11).
  24. Transfer foil according to any one of Claims 15 to 23, characterized in that the transfer lamina (11) includes an adhesive layer (6), the adhesive layer (6) being arranged on that side of the transfer lamina (11) which is remote from the carrier foil.
  25. Use of a transfer foil according to any one of Claims 15 to 24 for forming security elements on data carriers, more particularly value-bearing documents such as identity cards, tickets or banknotes, structural elements or decorative elements, more particularly in architecture or other technical fields, packaging materials, more particularly in the pharmaceutical or food industry and components in the electrical or electronics industry.
EP05761989A 2004-06-28 2005-06-23 Method for producing a metallic coating in certain areas of a substrate, transfer film and use thereof Not-in-force EP1765587B1 (en)

Applications Claiming Priority (2)

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DE102004031099A DE102004031099B4 (en) 2004-06-28 2004-06-28 Method for producing a zone-wise metallization
PCT/DE2005/001136 WO2006000201A1 (en) 2004-06-28 2005-06-23 Method for producing a metallic coating in certain areas of a substrate, transfer film and use thereof

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EP1765587B1 true EP1765587B1 (en) 2010-04-14

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JP (1) JP4746614B2 (en)
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DE102007024715B4 (en) * 2007-05-25 2009-04-09 Leonhard Kurz Gmbh & Co. Kg Process for producing a film and a multilayer film
DE102007032250B3 (en) * 2007-07-11 2008-12-18 ROWO Coating Gesellschaft für Beschichtung mbH Liquid i.e. water, leakage detecting device i.e. humidity sensor, for e.g. washing machine, has conductor paths present on side of surface unit, where one side of surface unit is flat while another side of surface unit is rough
DE102010002252A1 (en) * 2010-02-23 2011-08-25 JENOPTIK Laser GmbH, 07745 Method for applying soft solder to a mounting surface of a component
JP6314476B2 (en) * 2013-12-25 2018-04-25 凸版印刷株式会社 Transfer laminated media and printed matter
DE102015104416A1 (en) * 2015-03-24 2016-09-29 Leonhard Kurz Stiftung & Co. Kg Multilayer body and method for its production
RU2597373C1 (en) * 2015-04-29 2016-09-10 федеральное государственное автономное образовательное учреждение высшего образования "Санкт-Петербургский национальный исследовательский университет информационных технологий, механики и оптики" (Университет ИТМО) Method of producing metal films with given shape
GB2539389B (en) * 2015-06-10 2017-12-06 De La Rue Int Ltd Image arrays for security devices and methods of manufacture thereof

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US4232077A (en) * 1979-02-22 1980-11-04 Fritz Meisel Hot-stamping film, and process and apparatus for its manufacture
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US4687680A (en) * 1983-12-28 1987-08-18 Oike Industrial Co., Ltd. Stamping foil
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US5270078A (en) * 1992-08-14 1993-12-14 E. I. Du Pont De Nemours And Company Method for preparing high resolution wash-off images
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US6248198B1 (en) * 1996-05-27 2001-06-19 New Toyo Aluminium Paper Product Co. (Pte) Ltd. Process for manufacture of a laminated sheet
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US7833582B2 (en) 2010-11-16
EP1765587A1 (en) 2007-03-28
JP4746614B2 (en) 2011-08-10
JP2008504153A (en) 2008-02-14
CN101035672A (en) 2007-09-12
US20080095956A1 (en) 2008-04-24
DE102004031099A1 (en) 2006-01-26
WO2006000201A1 (en) 2006-01-05
CN101035672B (en) 2012-05-23
RU2007103171A (en) 2008-08-10
ATE464178T1 (en) 2010-04-15
DE102004031099B4 (en) 2006-07-27
DE502005009420D1 (en) 2010-05-27
RU2378120C2 (en) 2010-01-10

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