EP1357226A2 - Substrats avec couches électriquement conductrices - Google Patents

Substrats avec couches électriquement conductrices Download PDF

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Publication number
EP1357226A2
EP1357226A2 EP03008537A EP03008537A EP1357226A2 EP 1357226 A2 EP1357226 A2 EP 1357226A2 EP 03008537 A EP03008537 A EP 03008537A EP 03008537 A EP03008537 A EP 03008537A EP 1357226 A2 EP1357226 A2 EP 1357226A2
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EP
European Patent Office
Prior art keywords
electrically conductive
layer
substrates
layers
polymer
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.)
Granted
Application number
EP03008537A
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German (de)
English (en)
Other versions
EP1357226A3 (fr
EP1357226B1 (fr
Inventor
Hans Hermann Kammerer
Fritz Dr. Kastner
Matthias Müller
Martin Dr. Bergsmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hueck Folien GmbH
Original Assignee
Hueck Folien GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from AT3082003A external-priority patent/AT504538B1/de
Application filed by Hueck Folien GmbH filed Critical Hueck Folien GmbH
Publication of EP1357226A2 publication Critical patent/EP1357226A2/fr
Publication of EP1357226A3 publication Critical patent/EP1357226A3/fr
Application granted granted Critical
Publication of EP1357226B1 publication Critical patent/EP1357226B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/29—Securities; Bank notes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/48—Elements suited for physical verification, e.g. by irradiation

Definitions

  • the invention relates to substrates with electrically conductive layers, methods and a device for their production and their use.
  • security elements for security documents which have characters which are hidden in incident light, are recognizable in transmitted light and which are also designed to be electrically conductive, the electrically conductive material being present over the entire surface of at least one surface of the security element and is transparent or semi-transparent at least in partial areas and is arranged above and / or below the characters.
  • the electrically conductive material is always on the surface of the security feature.
  • the transparent or semi-transparent material is realized either by an indium tin oxide layer or by sputtering on a metal layer, in particular an aluminum layer.
  • the invention therefore relates to substrates with at least one electrical conductive layer, characterized in that the electrically conductive Layer (s) consist of electrically conductive polymers.
  • the polymers can be applied to a carrier substrate in the form of a dispersion or in the form of their monomers or prepolymers with subsequent application of an initiator and / or catalyst and / or catalyst or already in a mixture with an initiator and / or catalyst and / or catalyst.
  • the electrically conductive monomers or polymers can be applied in any known conventional manner, for example by spin coating, brushing on, vapor deposition, by printing (gravure printing, flexographic printing, screen printing, offset printing, digital printing and the like) by spraying, sputtering or roller application techniques.
  • carrier substrates also paper or composites with paper, for example, composites with plastics with a grammage 20-500 g / m 2, preferably 40-200 g / m 2. be used.
  • woven or non-woven fabrics such as continuous fiber non-woven fabrics, staple fiber non-woven fabrics and the like, which can optionally be needled and / or calendered, can be used as carrier substrates.
  • Such fabrics or nonwovens preferably consist of plastics, such as PP, PET, PA, PPS and the like, but fabrics or nonwovens made of natural, optionally treated fibers, such as viscose fibers, can also be used.
  • the nonwovens or fabrics used have a weight per unit area of approximately 20 g / m 2 to 500 g / m 2 . If necessary, the nonwovens or fabrics must be surface-treated.
  • FIG. 1 shows a special arrangement for applying the conductive polymers (as a dispersion of the polymers or as a mixture of monomer and initiator and / or catalyst and / or catalyst).
  • Fig.2 is another Possibility of applying the monomer and the initiator and / or Catalyst and / or catalyst shown in Figure 3 a way to Application of two successive layers of the electrically conductive Polymers
  • Fig. 4 a scheme for the preparation of the washing liquid and in 5 and 5a an embodiment of the invention
  • 1 means the carrier substrate, 2 a storage vessel for the polymer solution or dispersion, or for the mixture of the monomer with the catalyst or the monomer, 2a the application device for the catalyst (if only that in the storage vessel 2 Monomer is provided), 2b the storage vessel for the application of the second polymer layer, 3 a transfer roller, 4 a doctor blade, 5 a drying device (IR, UV or convection dryer), 6 the washing area with the following simultaneously or alternatively usable units 6a spray nozzles, 6b a brush or felt and 6c an air knife and 7 an optional blow molding or dryer.
  • 8 means water treatment (also metering in ions in the form of salts), 9 pressure control, 10 a pump, 11 the washing process, 12 a filter, 13-17 ion exchanger, 18 waste water disposal.
  • the storage vessel 2 or 2b consists of an outer tub 21 and an inner tub 22 with a return plate 22a.
  • 23 means the inflow of the monomer / initiator and / or catalyst and / or catalyst mixture from a storage (mixing) container 23a via a pump 23b and a filter 23c
  • 24 means the outflow of the monomer / initiator and / or catalyst and / or catalyst mixture from the outer tub 22 into the storage container.
  • 3a means a submersible cylinder and 3 the transfer cylinder.
  • the polymers can be applied to the carrier material in the form of a dispersion in a dispersant.
  • Baytron® P from Bayer, for example, can be used as a commercially available electrically conductive polymer suspension. (Fig. 1 and 5).
  • suitable dispersants are inert solvents, preferably aqueous solvents or alcohols, such as i-propanol.
  • matrix polymers for example water-soluble polyesters, polyurethanes, polystyrene sulfonates, polyacrylates or ethylene acrylate copolymers, can also be added to the polymer dispersions as matrix polymers.
  • polyethylene dioxythiophene with polystyrene sulfonate can be used as the matrix polymer.
  • the particle size of the polymers in the dispersion is preferably 20- 500 nm.
  • Fig. 5 23a which is preferably double-walled and temperature-controlled in order to adjust the polymer dispersion to an appropriate temperature, via a pump 23 b and a filter 23 c in the temperature-controlled inner tub 22 of the reservoir 2 (from Fig. 1) promoted.
  • a distributor tunnel 25 and the distributor plate 26 the with regularly arranged openings is provided, evenly distributed.
  • the inner tub has the shape of an approximately on the inner surface Half cylinder, this surface is dimensioned so that the Dip cylinder 3a at a defined constant distance from the inner surface of the reservoir 2 can intervene.
  • the inner tub 22 engages the submersible cylinder 3a with approximately 1 / 3-1 / 2 of its circumference the dispersion conveyed into the inner tub.
  • the temperature controlled The inner tub is dimensioned so that it is on the drain 24 of the surrounding temperature-controlled outer side facing away in about the dimension of a half cylinder, but its shape essentially continuing return plate up to a height of at least half of the Has diameter up to about 2/3 of the diameter of the immersion cylinder.
  • the monomer in Storage vessel 2 provided and possibly analogous to that shown in Fig. 5 Embodiment of the application device applied to the carrier substrate become.
  • the initiator and / or catalyst and / or catalyst or possibly the additional catalyst is provided in storage vessel 2a and on top of it applied to the carrier substrate, preferably a Excess initiator and / or catalyst and / or catalyst applied is used to achieve complete polymerisation of the polymer, as in the following particularly preferred embodiment described in more detail.
  • the drying process takes place again Washing process and possibly another drying process (as in the subsequent particularly preferred embodiment of the method described in more detail)
  • the corresponding Monomer or prepolymer preferably with the initiator and / or catalyst And / or catalyst (and possibly with an additional catalyst) mixed and applied to the carrier substrate (analog. Fig. 1, wherein in Storage vessel 2 the monomer / initiator and / or catalyst mixture provided).
  • the monomer / initiator and / or catalyst mixture is then in this case in (strongly) diluted solution.
  • Fe (III) toluenesulfonate is particularly preferred as initiator / catalyst used.
  • Fe (III) toluenesulfonate is a radical initiator or catalyst, which also initiates a redox reaction during the polymerization.
  • the Fe (III) ion acts as an initiator and the toluene sulfonate forms the matrix in the conductive polymer
  • ethylenedioxythiophene is used as a monomer, for example Baytron® M or Baytron® M-V2 from Bayer, and Fe (III) toluenesulfonate, for example Baytron® C types, for example Baytron® CB-40 from Bayer, as initiator and / or
  • the catalyst used is on the carrier substrate after the polymerization existing polymer polyethylene dioxythlophene / toluenesulfonate (PEDT-TS; P-DOT).
  • the initiator and / or catalyst in particular Fe (III) toluenesulfonate, e.g. Baytron® CB 40, from Bayer in large excess compared to Monomer resp. Prepolymer (e.g. ethylenedioxythiophene, such as Baytron® M or Baytron® M-V2 from Bayer).
  • the weight ratio of The monomer or prepolymer to initiator and / or catalyst is approximately 1:20 - 1: 100, preferably 1:50 to 1:80.
  • the excess of initiator and / or Catalyst ensures a perfect and safe implementation of the total monomer even during shorter available reaction times, which ensures that there are no harmful residues remain. Furthermore, this excess of initiator and / or Optimal film formation achieved catalyst.
  • the polymerization takes place depending on the solvent used already at the time when a temperature is reached that a Evaporation of the solvent causes.
  • a premature or too strong Polymerization prior to application to the carrier substrate in the Storage vessels, or a too rapid polymerization immediately after the Avoiding application to the carrier substrate is dependent on the temperature prevailing in the storage vessels advantageously from the provided storage containers of monomer or solvent as required replenished via a pump, with the addition of the solvent (for example an alcohol such as propanol or n-butanol) should be that after the polymerization not large amounts of Solvents remain in the layer, which are then removed must, so a balanced metering takes place.
  • the unwanted polymerization but by metering in the solvent controlled diluted monomer present
  • early polymerization can also be controlled precisely the temperature in the storage containers and in the applicator prevented are cooled, submersible cylinders or transfer and application cylinders if necessary or should be heated.
  • the polymerization takes place at Temperatures of 50 - 150 ° C, preferably at 80 - 120 ° C instead.
  • Excess initiator and / or catalyst and possibly catalyst residues and others contaminating reaction products can also be removed in situ be, or optionally subsequently by treatment with a Solvents, for example water, demineralized water, deionized Water, alcohols such as ethanol, propanols, butanols and the like or Water / solvent mixtures are removed from the layer.
  • a Solvents for example water, demineralized water, deionized Water, alcohols such as ethanol, propanols, butanols and the like or Water / solvent mixtures are removed from the layer.
  • the initiator and / or excess catalyst is preferred by water removed, for example by reverse osmosis, ion exchanger, distillation or physical water treatment plants.
  • the reaction can be influenced during the washing process by a defined setting of the ion content of the water, in particular the content of alkali and / or alkaline earth ions.
  • a defined setting of the ion content of the water in particular the content of alkali and / or alkaline earth ions.
  • the water treated as described above is therefore optionally adjusted to a defined ion content by adding alkali and / or alkaline earth ions in the form of salts, for example Na salts, for example NaCl or alkaline earth metal salts such as Mg salts, for example MgCl 2 .
  • alkali and / or alkaline earth ions in the form of salts, for example Na salts, for example NaCl or alkaline earth metal salts such as Mg salts, for example MgCl 2 .
  • the washing process is preferably carried out by applying the selected one Washing liquid by means of one or more nozzle bars, where preferably pressure and angle of those striking the coating Wash liquid are adjustable.
  • the excess water on the polymer coating is drained through squeeze, wipe, dry, by suitable devices, such as Squeezing devices, drying devices, air knife, or Extraction units removed and fed into a recycling circuit.
  • the water flowing out of the process is preferably circulated, fresh water can be added if necessary.
  • Initiator or initiator and catalyst saturated wastewater is over a Filter system and then via ion exchanger and / or through Prepared distillation.
  • ion exchanger can further preferably be a group of several, preferably 1-5 Ion exchangers are used, for example at least one ion exchanger is in operation, another in stand-by mode and another in regeneration mode.
  • Volatile constituents can then also be removed if necessary Drying with an IR dryer, a convection dryer and the like be removed.
  • the electrically conductive polymer layers can be used depending on the use have a thickness of 0.1-50 ⁇ m, preferably 0.5-10 ⁇ m. For certain uses are thinner layers of 0.001 - 50 ⁇ m, preferably 0.05 - 10 ⁇ m easily producible.
  • the layers according to the invention are extremely conductive.
  • the Stretchability of the layer may vary depending on the polymerization process can be controlled variably.
  • the electrically conductive polymer layers are generally temperature resistant, temperature resistances of> 100 ° C may occur can be achieved.
  • the electrically conductive polymers can also be pigmented, all of them known pigments are suitable, the transparency should not be clear are influenced, however, are highly opaque or coloring pigments such as Carbon black or graphite not suitable.
  • the proportion of pigments in the solid can be up to 40%.
  • the carrier material can improve the adhesion beforehand of the conductive polymer used treated with an adhesion promoter become. In general, however, especially when using the in situ Polymerization of the monomers or prepolymers adhere to the electrical conductive polymers on all carrier substrates definitely more than satisfying.
  • the electrically conductive polymers can be either full or partial be present on the carrier material.
  • Linear or analog structures have a conductivity directed in a preferred direction in accordance with the orientation of the structures.
  • these structures ensure additional security against destruction by transverse cracks in this layer and, if necessary, above and / or below it, since these are prevented from tearing at the gaps. If such an electrically conductive layer is protected by an additional layer, for example a lacquer layer or by lamination, the spaces or recesses ensure improved sealing of the conductive polymer layer.
  • These structures may also represent 2-dimensional coding.
  • the electrically conductive polymer layers are mechanical and are thermally very stable, but may be sensitive to moisture, these layers are preferably not directly on the surface of the substrate.
  • the different widths or Can have shapes and possibly also at different angles Basic structure can be arranged, connected.
  • the widths of the lines, waves or zigzag structures or Guilloches can, for example, 0.05-10 mm, preferably 0.1-0.3 mm of the cross connections 0.5 to 100 mm, preferably 1 to 10 mm.
  • the electrically conductive monomers or polymers can be applied any known conventional manner, for example by spin coating, Spreading, evaporation, by printing, (gravure, flexo, Screen printing, offset printing, digital printing and the like) by spraying, Sputtering or roller application techniques.
  • a solvent-soluble paint or a soluble varnish on the carrier substrate or any already on it existing layers are applied. Then the conductive Polymer applied to this layer, whereupon the soluble color in the not coated areas using the appropriate solvent, is removed with mechanical support if necessary.
  • a corresponding adhesion promoter can also be partially in the desired shape can be applied to the carrier substrate, then the electrically conductive polymer is applied over the entire surface, whereupon the Polymer in those areas where there is no adhesion promoter appropriate measures based on the basic adherence of the electrical conductive polymers are matched, can be removed again.
  • the electrically conductive polymer layer can also be adhesive or can be set for release.
  • the invention can be electrical conductive polymer layers also in connection with an inorganic preferably metallic or pigmented conductive layer especially be applied advantageously. This not only improves the electrical conductive properties of the coated substrate but also an additional assurance of the perfect function and identifiability.
  • a multi-layer structure of a full or partial layer of one conductive polymers with line-shaped, wavy ones printed over them and like structures of the same polymer result in different ones Conductivities in different directions, for example parallel or across the machine direction, but also at any angle to Machine direction.
  • the full-surface polymeric conductive base layer a corresponding depth variable gravure cylinder, in different Executed thickness, angle-dependent conductivities are achieved.
  • the polymeric conductive base layer and the second one applied over it polymeric conductive layer can optionally by a Insulator layer to be separated.
  • the electrically conductive (polymeric) layer (s) are preferably not located in direct contact with metallic layers and will be separated by an insulator layer.
  • the electrically conductive polymer layers as well optionally the additional inorganic metallic and / or pigmented electrically conductive layers encoded as patches and thus can also be applied in a machine-readable and / or structured manner. Can also the electrically conductive polymer layers then inline or offline be shaped.
  • the carrier substrate can already have functional or decorative layers have, or there may be more after application of the conductive layer Layers are applied.
  • the carrier substrates can additionally have a lacquer layer that unstructured or structured, for example, can be shaped.
  • the Lacquer layer can be, for example, a release-capable transfer lacquer layer, it can be cross-linked or by radiation, for example UV radiation be cross-linkable and scratch-resistant and / or antistatic.
  • Suitable are both aqueous and solid coating systems, especially also Lacquer systems based on polyester acrylate or epoxy acrylate rosin, Acrylate, alkyd, melamine, PVA, PVC, isocyanate, urethane systems, the can be conventional and / or reactive curing and / or radiation curing.
  • compositions are used.
  • the composition of each Layers can vary in particular according to their task, i.e. whether the serve individual layers exclusively for decorative purposes or one functional layer or whether the layer is both a decorational should also be a functional layer.
  • These layers can be pigmented or unpigmented.
  • pigments all known pigments, such as titanium dioxide, zinc sulfide, Kaolin, ITO, ATO, FTO, aluminum, chromium and silicon oxides as well as colored ones Pigments are used.
  • solvent-based paint systems as Systems without solvents can also be used.
  • the functional layers can have certain magnetic, have chemical, physical and optical properties.
  • paramagnetic, diamagnetic and also ferromagnetic materials such as iron, nickel and Cobalt or their compounds or salts (for example oxides or Sulfides) can be used.
  • Magnetic pigment paints with pigments based on Fe oxides, iron, nickel cobalt and their alloys, barium or cobalt ferrites, hard and soft magnetic iron and steel types in aqueous and / or steel types are particularly suitable for use in connection with the electrically conductive polymer layers according to the invention.
  • dispersions containing solvents are i-propanol, ethyl acetate, methyl ethyl ketone, methoxypropanol and mixtures thereof.
  • the pigments are preferably introduced in acrylate polymer dispersions with a molecular weight of 150,000 to 300,000, in nitrocellulose, acrylate urethane dispersions, acrylate styrene or PVC-containing dispersions or in solvent-containing dispersions of this type.
  • the optical properties of the layer can be determined by visible dyes or pigments, luminescent dyes or pigments that are visible, fluoresce or phosphoresce in the UV or IR range, Effect pigments, such as liquid crystals, pearlescent, bronzes and / or multilayer color change pigments and heat-sensitive colors or pigments influence. These can be used in all possible combinations.
  • phosphorescent pigments can also be used alone or in Combination with other dyes and / or pigments can be used.
  • the color or the color lacquer used can be soluble in a solvent, preferably in water, but a color soluble in any solvent, for example in alcohol, esters and the like, can also be used become.
  • the color or the colored lacquer can be conventional compositions based on natural or artificial macromolecules.
  • the color can be pigmented or unpigmented. All known pigments can be used as pigments. TiO 2 , ZnS, kaolin and the like are particularly suitable.
  • a soluble color layer is used, this can optionally be removed after applying a further layer in the process according to the invention by means of a suitable solvent which is matched to the composition of the color layer, in order to be able to produce codes in the form of characters and / or patterns of any possible type.
  • the paint layer is then removed using a suitable solvent which is matched to the composition of the paint layer.
  • the paint application is preferably water-soluble. If necessary, the detachment can be supported by mechanical action.
  • the thickness of this Layer is about 0.01 - 5 microns.
  • Insulator layers can also be applied, for example.
  • insulators are organic substances and their derivatives and compounds, for example paint and lacquer systems, for example epoxy, polyester, rosin, acrylate, alkyd, melamine, PVA, PVC, isocyanate, urethane systems, which are radiation-curing can be suitable, for example by heat or UV radiation.
  • Layers of this type can be used in particular in the production of multilayer structures, for example for printed circuit boards between two or more electrically conductive polymer layers and / or electrically conductive metallic and / or pigmented layers which have to be separated from one another.
  • the thickness of the functional layers is generally about 0.001 to 50 microns, preferably 0.1 to 20 microns.
  • partial or full-area metallic layers can be present on the carrier substrate or subsequently applied.
  • This layer consists of a metal, a metal compound or an alloy, wherein these metallic layers can also represent inorganic electrically conductive layers.
  • Layers of A1, Cu, Fe, Ag, Au, Cr, Ni, Zn and the like are suitable as the metal layer.
  • suitable metal compounds are oxides or sulfides of metals, in particular TiO 2 , Cr oxides, ZnS, ITO, ATO, FTO, ZnO, Al 2 O 3 or silicon oxides.
  • Suitable alloys are, for example, Cu-Al alloys, Cu-Zn alloys and the like.
  • All of these layers can be both full and partial, register and register-accurate, possibly also at least partially overlapping with the existing layers can be applied.
  • filtered air with defined air humidity is directed onto the printing cylinder at the same speed, as a result of which the thin layers on the cylinder dry and can no longer be applied to the carrier substrate.
  • an IR drying device situated over the entire width can also be used.
  • toning residues can also be removed, for example, by using a plasma (low-pressure or atmospheric plasma), corona or flame process.
  • High-energy plasma for example Ar or Ar / O 2 plasma, cleans the surface of toning residues in the printing inks.
  • the additional application of such a process is particularly advantageous when applying metallic layers.
  • the surface is activated. Terminal polar groups are created on the surface. This improves the adhesion of metals and the like to the surface.
  • a thin metal or metal oxide layer can be applied as an adhesion promoter, for example by sputtering or vapor deposition, simultaneously with the application of the plasma or corona or flame treatment.
  • Cr, Al, Ag, Ti, Cu, TiO 2 , Si oxides or chromium oxides are particularly suitable.
  • This adhesion promoter layer generally has a thickness of 0.1 nm - 5 nm, preferably 0.2 nm - 2 nm, particularly preferably 0.2 to 1 nm.
  • the product is therefore possibly after appropriate packaging as a security element in data media, especially value documents such as ID cards, cards, banknotes or labels, seals and the like suitable, but also as packaging material, for example in the pharmaceutical and food industries, for example in the form Blister films, folding boxes, covers, film packaging and the like.
  • Products of this type are also particularly suitable for Applications in the electronics industry, for example as printed circuit boards, RF antennas for transponders and the like, displays, flexible circuits, medical facilities, electrode structures, as heatable foils, for windscreens, for example, as a transparent reflective layer under holograms and / or structured layers and the like.
  • the width of the stripes or threads can preferably be 0.05-10 mm.
  • Adhesion promoter (A 1120, OSI)
  • a dispersion of 2% polyethylene dioxythiophene via a transfer roller (Particle size 100 nm in the dispersion) with 2% polystyrene sulfonate in water / i-propanol as a dispersing agent over the entire surface in a layer thickness of 3 ⁇ m applied. Then the applied polymer layer at 110 ° C. dried.
  • the film thus produced has a conductivity of 800 ⁇ / square conductive layer has a transparency of 87%
  • a mixture is then applied to the film produced analogously to Example 1 of ethylenedioxythiophene and Fe (III) toluenesulfonate as initiator in Weight ratio 1:60 at a temperature of 110 ° C in the gravure process applied and polymerized This mixture polymerizes in situ and is then to remove catalyst residues with water treated. The layer is then dried and a conventional one Protective lacquer layer applied.
  • the conductive film thus produced has a conductivity of 220 ⁇ / square and the two conductive layers together have a transparency of 82% on.
  • fluorescent paint layer shows no influence on the conductivity or Transparency of the free areas of the conductive layers.
  • a partial layer made of Baytron® M and Baytron® CB-40 in a weight ratio of 1:60 dissolved in n-butanol is applied to a 6 ⁇ m polyester film in accordance with the process described in FIGS. 1 and 5a.
  • the partial layer has a linear structure 0.1 mm wide at a distance of 0.1 mm.
  • An opaque printing ink is partially applied to this layer in the form of any characters.
  • the substrate is then cut into threads with a width of 1 mm, which means that there are an average of 5 line structures on one thread.
  • the directional conductivity is 215 ⁇ / square.
  • the film produced according to Example 3 is coated with a 10 ⁇ m PET film with a 0.5 ⁇ m partial layer consisting of a magnetic printing ink based on Fe 3 O 4 in an acrylate polymer dispersion and a 0.2 ⁇ m layer made of a fluorescent printing ink laminated using a standard laminating adhesive.
  • the conductivity was 215 ⁇ / square, the magnetic properties were determined with 330 nW / m at a coercivity of 250 Oerstedt.

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  • Business, Economics & Management (AREA)
  • Accounting & Taxation (AREA)
  • Finance (AREA)
  • Laminated Bodies (AREA)
  • Non-Insulated Conductors (AREA)
  • Silicon Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Rolls And Other Rotary Bodies (AREA)
  • Paints Or Removers (AREA)
EP03008537A 2002-04-22 2003-04-12 Substrats avec couches électriquement conductrices Expired - Lifetime EP1357226B1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
AT6142002 2002-04-22
AT6142002 2002-04-22
CH2702003 2003-02-20
CH2702003 2003-02-20
AT3082003 2003-03-03
AT3082003A AT504538B1 (de) 2003-03-03 2003-03-03 Substrate mit elektrisch leitfähigen schichten

Publications (3)

Publication Number Publication Date
EP1357226A2 true EP1357226A2 (fr) 2003-10-29
EP1357226A3 EP1357226A3 (fr) 2004-01-07
EP1357226B1 EP1357226B1 (fr) 2010-08-11

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EP03008537A Expired - Lifetime EP1357226B1 (fr) 2002-04-22 2003-04-12 Substrats avec couches électriquement conductrices

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EP (1) EP1357226B1 (fr)
AT (1) ATE477371T1 (fr)
DE (1) DE50312962D1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004111338A1 (fr) * 2003-06-17 2004-12-23 Hueck Folien Ges.M.B.H Elements de securite a attributs perceptibles visuellement et lisibles par machine
WO2005012442A1 (fr) * 2003-07-30 2005-02-10 Datalase Ltd. Compositions pouvant etre marquees au laser
EP1562154A1 (fr) * 2003-12-29 2005-08-10 Hueck Folien Ges.m.b.H substrats avec couches polymeres conductrices d' electricite en polythiophene ou ses derives
WO2006042568A1 (fr) * 2004-10-20 2006-04-27 Hueck Folien Ges.M.B.H Substrats comportant des couches electroconductrices
EP1841004A1 (fr) 2006-03-29 2007-10-03 Hueck Folien Ges.m.b.H Antenne pour transpondeur sur un substrat à revêtement antistatique
US8048605B2 (en) 2001-03-16 2011-11-01 Datalase Ltd Laser-markable compositions
US8753791B2 (en) 2001-03-16 2014-06-17 Datalase Ltd. Laser-markable compositions
EP2966221A1 (fr) * 2014-07-07 2016-01-13 Electronics and Telecommunications Research Institute Papier d'impresssion de sécuritè basè sur un identificateur de radio-frequence sans puce et la methode de fabrication de la meme
US10671192B2 (en) 2011-07-08 2020-06-02 Heraeus Deutschland GmbH & Co. KG Process for the production of a layered body and layered bodies obtainable therefrom

Family Cites Families (8)

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US8048605B2 (en) 2001-03-16 2011-11-01 Datalase Ltd Laser-markable compositions
US8753791B2 (en) 2001-03-16 2014-06-17 Datalase Ltd. Laser-markable compositions
US8936901B2 (en) 2001-03-16 2015-01-20 Datalase Ltd. Laser-markable compositions
WO2004111338A1 (fr) * 2003-06-17 2004-12-23 Hueck Folien Ges.M.B.H Elements de securite a attributs perceptibles visuellement et lisibles par machine
WO2005012442A1 (fr) * 2003-07-30 2005-02-10 Datalase Ltd. Compositions pouvant etre marquees au laser
US8698863B2 (en) 2003-07-30 2014-04-15 Datalase Ltd. Laser-markable compositions
EP1562154A1 (fr) * 2003-12-29 2005-08-10 Hueck Folien Ges.m.b.H substrats avec couches polymeres conductrices d' electricite en polythiophene ou ses derives
WO2006042568A1 (fr) * 2004-10-20 2006-04-27 Hueck Folien Ges.M.B.H Substrats comportant des couches electroconductrices
EP1841004A1 (fr) 2006-03-29 2007-10-03 Hueck Folien Ges.m.b.H Antenne pour transpondeur sur un substrat à revêtement antistatique
US10671192B2 (en) 2011-07-08 2020-06-02 Heraeus Deutschland GmbH & Co. KG Process for the production of a layered body and layered bodies obtainable therefrom
EP2966221A1 (fr) * 2014-07-07 2016-01-13 Electronics and Telecommunications Research Institute Papier d'impresssion de sécuritè basè sur un identificateur de radio-frequence sans puce et la methode de fabrication de la meme
US9368010B2 (en) 2014-07-07 2016-06-14 Electronics And Telecommunications Research Institute Security printing paper based on chipless radio frequency tag and method of manufacturing the same

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EP1357226A3 (fr) 2004-01-07
DE50312962D1 (de) 2010-09-23
EP1357226B1 (fr) 2010-08-11
ATE477371T1 (de) 2010-08-15

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