WO2006042568A1 - Substrates comprising electroconductive layers - Google Patents

Substrates comprising electroconductive layers Download PDF

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Publication number
WO2006042568A1
WO2006042568A1 PCT/EP2004/011855 EP2004011855W WO2006042568A1 WO 2006042568 A1 WO2006042568 A1 WO 2006042568A1 EP 2004011855 W EP2004011855 W EP 2004011855W WO 2006042568 A1 WO2006042568 A1 WO 2006042568A1
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WO
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Patent type
Prior art keywords
characterized
electrically conductive
layer
according
sheet material
Prior art date
Application number
PCT/EP2004/011855
Other languages
German (de)
French (fr)
Inventor
Friedrich Kastner
Martin Bergsmann
Evelyne Wagner
Original Assignee
Hueck Folien Ges.M.B.H
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Classifications

    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/09Use of materials for the metallic pattern or other conductive pattern
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B42BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42DBOOKS; 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
    • B42D25/00Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/20Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/29Securities; Bank notes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04Coating
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H21/00Non-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
    • D21H21/14Non-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
    • D21H21/40Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/48Elements suited for physical verification, e.g. by irradiation
    • GPHYSICS
    • G07CHECKING-DEVICES
    • G07DHANDLING OF COINS OR OF PAPER CURRENCY OR SIMILAR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
    • G07D7/00Testing specially adapted to determine the identity or genuineness of paper currency or similar valuable papers or for segregating those which are alien to a currency or otherwise unacceptable
    • G07D7/02Testing electrical properties of the materials thereof
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124Intrinsically conductive polymers
    • H01B1/127Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/14Security printing
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H21/00Non-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
    • D21H21/14Non-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
    • D21H21/40Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/42Ribbons or strips
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • H05K1/0393Flexible materials
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03Conductive materials
    • H05K2201/032Materials
    • H05K2201/0329Intrinsically conductive polymer [ICP]; Semiconductive polymer

Abstract

The invention relates to substrates comprising electroconductive layers consisting of electroconductive polymers. Said electroconductive polymers can be present on the substrate optionally in the presence of other electroconductive and/or functional and/or decorative layers. The substrates are used especially, inter alia, as security elements, as components in the electronic industry, and as decorative elements.

Description

Substrates with electrically conductive layers

The invention relates to substrates with electrically conductive layers, method and apparatus for their preparation and their use.

In the production of coated substrates typically conductive paint or varnish to be used for printing of electrically conductive layers. The paints or varnishes, electrically conductive pigments such as carbon black, graphite, silver and the like are thereby added in general. However, the inks and coatings provided with these pigments are clearly visible after printing, especially on transparent substrates.

In various applications, however, it is undesirable that the applied electrically conductive layers are immediately recognizable. This is especially true for the use in security features for data carriers, valuable documents and products of all kinds.

From EP 0426801 B, for example, security elements for security documents are known that have the characters that are hidden in the incident light, are recognizable in transmitted light and which are also made electrically conductive, the electrically conductive material over the entire area available on at least one surface of the security element, and is transparent or semitransparent at least in partial regions and is arranged above and / or below the mark. The electrically conductive material is always located at the surface of the security feature. In this case, the transparent or semi-transparent material is realized either by an indium tin oxide layer or by sputtering a metal layer, in particular an aluminum layer.

but in particular for security applications, certain requirements must be placed on the electrically conductive layer for a safe function and identification of the electrically conductive features, especially as regards the electric resistance, mechanical resistance, flexibility, extensibility, the temperature and chemical resistance, with the known solutions can not be satisfactorily achieved. In particular, when used as RF antennas for transponders, in anti-theft labels, smart cards, and the like, a safe function needs to be ensured.

From EP 1185422 B1 an optically variable security feature having diffractive structures is known, consisting of an electrically conductive polymer and at least one carrier film, a protective layer, a lacquer layer and a reflective layer, wherein the electrically conductive polymer is a arranged on different layers polyethylenedioxythiophene-polystyrenesulfonate is.

From WO 99/66128 electrical feature substances for integration in paper webs are known, as an electrically conductive transparent polymer polyethylene dioxythiophene polystyrene sulfonate is used.

However, the wording of the polyethylenedioxythiophene available polystyrene sulfonate polymer matrix have have that can not be changed in the application, to be accepted without serious disadvantages in the processing and application of polymer or negative effects on the quality of the coating only defined viscosities. However, the change or setting of a defined viscosity is particularly advantageous when the partial application of the conductive polymer is crucial. Depending on the motives, the desired layer thickness, conductivity and transparency of a different viscosity leads to the optimal result. For example, to print finer grid, ie fine structures in the printed image are low viscosities required to obtain precise contours and edges.

Further, polyethylenedioxythiophene printing process by in situ polymerization of the monomer, for example Baytron M with a catalyst, for example Fe (III) is known, toluenesulfonate printing technology to apply. Also in this method the setting of a defined viscosity to obtain a printed image with high edge sharpness is hardly possible because this serious disadvantages in the in situ Polymerisiation (insufficient polymerization and therefore low conductivity and clear staining of the layer) must be taken into account.

Further, it is desirable that security features as well as conductivity has an additional, preferably machine-readable feature to ensure increased protection against tampering. The currently known and used electrically conductive polymers are mostly transparent, but have other than the conductivity per se any additional property, which would meet these requirements. Additional, preferably machine-readable properties can currently only by suitable additives (e.g., dyes and the like) can be achieved.

Therefore, an object of the invention to provide substrates with electrically conductive polymeric layers, which additionally have independent of the line width, the desired characteristics mentioned above, namely, an additional machine-readable feature and high edge sharpness of the printed image.

Accordingly, the present invention provides substrates comprising at least one electrically conductive layer, characterized in that the electrically conducting layer (s) (s) from thiophene derivatives or a mixture of thiophene derivatives is (s) comprising at least one additional to the conductivity, physical, machine-readable feature has (s) and independent of the line width with high edge sharpness is printability (are).

Another object of the invention is a method for the production of substrates with at least one electrically conductive layer, characterized in that a monomer or prepolymer is applied to the carrier substrate and is polymerized in situ, wherein the initiator and / or catalyst may also be removed in situ or the polymers are applied as a dispersion to the carrier substrate.

Suitable poly-thiophene derivatives are alkyl, urethane, sulfonic acid, ether, ester, benzo- and aza (poly) thiophenes, such as polymers of the monomers or Ethylendioxythiophenmethanol; Benzoethylendioxythiophen; (Poly) - 3-hexylthiophene; Thieno (3,4-b) -1,4-dioxin-2-methanol, 2), 3-dihydro-; or 2H-thieno (3,4-b) (1, 4) dioxepin-3-d, 3,4-dihydro-.

These polymeric conductive coatings have other than the conductivity in each case an additional visually recognizable or machine-readable feature.

For example, the Polyethylendioxythiophenmethanol prepared in situ showing IR-reflecting properties,

Polythiophenether thermally induced thermochromic and fluorescent properties. Poly-3-hexylthiophene shows VIS reflection, similar to a metallic luster. In conjunction with a dielectric show Ethylendioxythiophenmethanol and ethylenedioxythiophene and derivatives thereof reversible electrochromic properties.

These properties can be modified, for example by mixtures with other poly-thiophene derivatives and expanded. Here, for example, targeted IR, diffuse or shiny metallic VIS or UV properties can be adjusted in defined band areas. Furthermore, a corresponding modification to increase the long-term stability contributes.

The liquid coatings have good solubility in solvents such as water, alcohols and in aromatics, for example, in IPA, butanol, or ethanol. Therefore, the viscosity of the coating composition upon application of the coating can be defined by adjusting the solids content and amount of solvent set. Thus, printing is both fine and coarse grid and / or line structures with a corresponding edge acuity (line width tolerance besipielweise. ± 0.01 mm).

The polymers can be applied to a carrier substrate in the form of a dispersion, or preferably in the form of their monomers or prepolymers, with subsequent application of an initiator and / or catalyst or already in a mixture with an initiator and / or catalyst.

The application of the electrically conductive monomers or polymers can take place in any known conventional manner, for example by spin coating, brushing, vapor deposition, by printing (gravure printing, flexographic printing, screen printing, offset printing, digital printing and the like) by spraying, sputtering, or roll coating techniques.

As carrier substrates include, for example carrier films, preferably flexible transparent plastic films, for example of PI, PP 1 MOPP, PE, PPS, PEEK, PEK, PEI, PAEK, LCP, PEN, PBT, PET, PA, PC, COC, POM, ABS, PVC , PTFE, ETFE, CTFE in question.

The carrier films preferably have a thickness of 5-700 .mu.m, preferably 5-200 .mu.m, particularly preferably of 5 - 50 microns.

Further, as the support substrate, metal foils, for example Al, Cu, Sn, Ni, Fe or stainless steel foils with a thickness of 5 - 200 microns, preferably 10 to 80 .mu.m, particularly preferably 20 - 50 microns are used. The foils can also be surface treated, coated or laminated, for example with plastics or lacquered. Further, as carrier substrates also paper or composites with paper, for example, composites with plastics with a grammage of 20 - 200 g / m 2, used - 500 g / m 2, preferably 40th

Furthermore, can be used as carrier substrates fabrics or nonwovens, such as endless fiber nonwovens, staple fiber nonwovens and the like, which may optionally be needle-punched or hydro-dynamic and / or calendered. Preferably, such woven or nonwoven fabrics made of plastics, such as PP, PET, PA, PPS and the like, but it may also be woven or nonwoven fabrics made of natural, possibly treated fibers, such as viscose fibers are used. The nonwoven or woven fabrics used have a grammage of about 20 g / m 2 to 500 g / m 2. If necessary, the nonwoven or woven fabrics have to be surface treated.

In Figure 1, a special arrangement for the application of the conductive polymers as a mixture of monomer and initiator and / or catalyst and / or catalyst) is shown. In Fig.2 a further possibility of application of the monomer and the initiator and / or catalyst and / or catalyst is shown in Figure 3 is a possibility for the application of two successive layers of the electrically conductive polymer, in Fig. 4 is a schematic for the preparation of washing liquid and in Fig. 5 and Fig. 5a is an embodiment of the applicator with the reservoir and provided as separate reservoirs Zudosiereinheiten invention.

In Figs. 1 to 3 1, the carrier substrate, 2 denotes a storage vessel for the mixture of the monomer with the catalyst or of the monomer 2a, the application device for the catalyst (when only the monomer is provided in the supply vessel 2), 2b the storage vessel for the application of the second polymer layer 3, a transfer roller 4, a doctor blade, 5 is a dryer means (IR, UV or convection), 6 the washing area with the following simultaneously or alternatively usable units 6a spray nozzles 6b, a brush or a felt and 6c an air knife and 7 an optional blowing strip or a dryer.

In FIG. 4, 8, the water treatment means (also metered addition of ions in

The form of salts), 9 is a pressure control, a pump 10, 11 to

Washing process, a filter 12, 13-17 ion exchanger, 18 the

Sanitation.

In Figs. 5 and 5a, a preferred coating apparatus (2 or 2b, and 3 as shown in Figures 1 -. 3) is shown with associated described in more detail below additional immersion cylinder 3a. In the preferred application device 2 and 2b, the reservoir of an outer tub 21 and inner tub 22 with a return plate 22a. 23 represents the feed of the monomer / initiator and / or catalyst and / or catalyst mixture from a supply (mixed) container 23a via a pump 23b and a filter 23 c, 24 denotes the flow of monomer / initiator and / or catalyst and / or catalyst mixture from the outer tub 22 in the reservoir. 3a represents a diving cylinder 3 and the transfer cylinder. 25 represents a distribution channel for the monomer / initiator and / or catalyst and / or catalyst mixture 26, the distributor plate of the distributor tunnel.

In Fig. 5a means 27 the supply container for the monomer and the reservoir 28 for the initiator and / or catalyst and the reservoir 29 for the solvent.

Here, 5 is preferably as shown in FIG. From a reservoir 23a, which is preferably double-walled and temperature controlled to set an appropriate temperature, via a pump 23 b, and a filter 23c in the temperature-controlled inner tub 22 of the hopper 2 (from Fig. 1) promoted. In the Innenwänne is applied mixture via a distributor tunnel 25 and the distribution plate 26, which is provided with regularly spaced openings uniformly distributed. The Inπenwanne has on the inner surface the shape of an approximately semi-cylinder, said surface being dimensioned so that the dipping cylinder 3a can engage in a defined constant distance from the inner surface of the reservoir. 2 Depending on the height of the filling in the inner tub 22 of the diving cylinder 3a is engaged in the inner tub supported in the mixture with about 1 / 3-1 / 2 of its circumference. The temperature-controlled inner tub is dimensioned so that it on the side remote from the spout 24 of the ambient temperature controlled outer tub side in about the dimension of a half-cylinder, however, the shape of which substantially continuously releasing return plate up to a height of at least half of the diameter up to about 2 / 3 has the diameter of the plunger cylinder.

The dive cylinder tackles the polymer dispersion of the inner tub and transfers it to the transfer cylinder. The excess mixture which is not absorbed by the transfer cylinder, now passes back over the outside of the inner tub in the outer tub 21st Likewise, that part that was the doctor blade 4 (in Fig.5 not shown) is not applied to the layup tool running, back into the outer tub.

Due to the orientation of the outer tub is not flat in one plane, but at a slight incline from the side opposite the outflow side of the tub to the side on which the drain is situated, the trapped in the outer tub 21 mixture of the entire paint applicator unit is back in out the reservoir 23a. So in the inner tub is always just out of the reservoir under a defined temperature and with the b defined by the pump 23 inflow rate charged mixture.

By avoiding the reflux of not using the following cylinder and the doctor applied mixture into the inner tub while the temperature mixture into the inner tub and air entry is avoided correctly held constant. Further, the temperature of the mixture in the inner tub can continuously via a temperature sensor (not shown in Fig.5) can be controlled.

Subsequently, the drying of the coated layer by the drying apparatuses 5 or the washing process in the washing station 6 for the removal of solvent residues (Fig.1) is carried out

but the monomers or prepolymers to form the electrically conductive polymers will be preferably applied and polymerized in situ (Fig. 2, 3 and 5a).

In this case can be, for example, UV is used as the initiator and / or catalyst both radical, as well as redox or photoinitiator and / or catalysts.

Both monomer and initiator and / or catalyst and / or catalyst are preferably provided in a solvent or dispersing agent, for example in an alcohol such as propanol or n-butanol.

Optionally, a catalyst such as a Ziegler-Natta may additionally be added to accelerate the reaction, catalyst, or a Pt - catalyst, then, if appropriate, and / or catalyst may be less, the added amount of initiator.

In one embodiment, as shown in Figure 2, provided the monomer in the storage vessel 2 and, if appropriate embodiment of the applicator shown in Figure 5 are applied to the carrier substrate analog in FIG.. The initiator and / or catalyst or, if appropriate, the additional catalyst is provided in storage vessel 2a and applied to the left on the carrier substrate monomer, preferably an excess of initiator and / or catalyst applied is to achieve a complete polymerization of the polymer, such as described in the following particularly preferred embodiment in more detail. After the polymerization, the drying operation, the washing operation and possibly a further drying operation is carried out in turn (as shown in the following particularly preferred embodiment of the inventive method described in more detail)

In the most preferred embodiment, the corresponding monomer or prepolymer is preferably with the initiator and / or catalyst (and optionally with an additional catalyst) and to the carrier substrate applied (similar to Fig. 1, wherein in the supply vessel 2, the monomer / initiator and / is provided or catalyst mixture).

The preferred embodiment of the applicator device in this case has, as shown in Fig. 5a, in addition to those shown in Fig. Elements shown in Figure 5 each have a reservoir for the monomer and a separate reservoir for the initiator and / or catalyst or initiator and / or catalyst or additional catalyst mixture and for the optionally additionally metered solvent. Preferably, the solvent is metered in over a viscosity regulator.

It is also possible in a storage container, a solution of monomer or prepolymer and an initiator and / or catalyst and to provide in a second storage vessel, if necessary, the solvent to be metered. The monomer / initiator and / or catalyst blend is then in this case in (strongly) diluted solution.

(III) is particularly preferred as an initiator / catalyst used Fe toluenesulfonate. Fe (III) -toluenesulfonate is a free-radical initiator or catalyst, which also initiates a redox reaction during the polymerization. The Fe (III) ion acts as initiator and the toluenesulfonate is in the conductive polymer matrix.

Thus, if ethylenedioxythiophene-methanol as a monomer, for example Baytron ® -OH Fa. Bayer, and Fe (III) -toluenesulfonate, for example Baytron ® C-types, for example Baytron ® CB-40 from Bayer, is used as initiator and / or catalyst, is which on the carrier substrate after the polymerization existing polymer polyethylenedioxythiophene-methanol / toluene.

In order to avoid any residues in the conductive layer is the initiator and / or catalyst, ie in particular Fe (III) -toluenesulfonate, for example Baytron ® CB 40, Fa. Bayer respectively in large excess compared to the monomer. Prepolymer used. The weight ratio of monomer or prepolymer to initiator and / or catalyst amounts to about 1: 5 - 1: 100, preferably 1: 8 to 1: 80th The excess of initiator and / or catalyst ensures a perfect and safe implementation of the entire monomer during a shorter reaction time available, thus it is ensured that no harmful residues remain. Furthermore, an optimum film formation is achieved by this excess of initiator and / or catalyst.

The polymerization takes place depending on the used solvent! already at the time in which a temperature is reached which causes evaporation of the solvent. To prevent premature or excessive polymerization prior to application to the carrier substrate into the storage vessels, or a too rapid polymerization immediately after application to the carrier substrate, is a function of the pressure prevailing in the storage vessel temperature advantageously of the intended storage containers monomer postdosed or solvent as necessary by using a pump, wherein, in the addition of the solvent (for example, an alcohol such as propanol or n-butanol) it should be ensured that after the polymerization does not remain large amounts of solvent in the layer which is subsequently must be removed, so a balanced metering takes place. Preferably, the polymerization is undesirable but is controlled by metering in the highly diluted solvent present in the monomer. By adjusting the solids content and the amount of solvent, and the temperature or by targeted prepolymerization in the paint bucket, the viscosity is adjusted manually or automatically defined.

By a known Fallviskosimeter with automatic

Solvent viscosity adjustment can be set and kept constant.

Alternatively, an early polymerization can also be prevented by accurate control of the temperature in the storage containers and applicator mechanism, said dip cylinder or carry and applicator cylinder should be optionally cooled or heated.

In accordance with FIGS. 5 and 5a designed applicator unit is therefore controlled reaction kinetics, by adjusting the proportions of the blend components or the temperature and simultaneously achieve a uniform homogenous application of the polymer dispersion and the monomer or the monomer / initiator and / or catalyst mixture ,

Depending on the solvent used is the polymerization at temperatures of from 50 - 15O 0 C, preferably at 80 - 13O 0 C instead.

Initiator and / or catalyst excess and, if necessary, catalyst residues and other contaminating reaction products can thereby also be removed in situ or, if appropriate, then by treatment with a solvent, 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 catalyst excess is preferably removed by water is prepared, for example by reverse osmosis, ion exchangers, distillation or physical water treatment plants. The reaction may be affected during the washing process by a defined setting of the lonengehalts of water, in particular the content of alkali and / or alkaline earth ions. methanol by the addition of water present in the ions to the oxygen atoms of the Ethylendioxythiophen- - units to form complexes, so that the configuration of the macromolecule is changed, and thus the band gap in the absorption spectrum and hence the absorption maximum is shifted. At the same time, the conductivity can be changed by this complex formation and, therefore, can be adjusted by the content of ions is defined in the water.

Therefore as described above treated water is such as MgCl 2 adjusted to a defined ionic content, if appropriate, by addition of alkali and / or alkaline earth ions in the form of salts, such as Na-salt, for example NaCl or alkaline earth metal salts such as Mg salts.

The washing process is preferably carried out by applying the selected washing fluid by means of one or more nozzle bars, preferably pressure and angle of incident on the coating washing liquid can be adjusted.

The excess water on the polymer coating by squeezing, wipe, dry, by suitable means, such as Abquetschvorrichtungen, drying devices, air knife, or

Suction units removed and taken to a Recyclierungskreislauf.

The effluent from the process water is preferably circulated, wherein fresh water may be added optionally as needed. With initiator or initiator and catalyst saturated waste water is via a filter system, and then over the ion exchanger and / or processed by distillation. In order to ensure continuous operation, can further preferably a group of several, preferably 1 - 5 ion exchangers are used, whereby, for example, is at least one ion exchanger in operation, another stand-by-Modυs and one in regeneration mode.

Optionally, a washing process with pure, purified as described above, fresh water can be connected in conclusion.

Volatile components may subsequently optionally also by drying with an infrared dryer, a convection dryer, and the like are removed.

The electrically conductive polymer layers may depending on the application each have a thickness of 0.1 - 50 microns, preferably 0.5 - 10 microns have. For certain uses are thinner layers from 0.001 to 50 .mu.m, preferably from 0.05 to 10 microns readily producible.

Furthermore, films of the invention are excellent conductive. The stretchability of the layer may vary depending on the polymerization and by adding a binder, such as, optionally crosslinked, for example of polyvinyl alcohols with melamine resins, are variably controlled. The finer morphology of the poly-thiophene derivatives, for example in particular also of the Pblyethylendioxythiophen-methanol in comparison to known thiophenes additionally ensures a constant conductivity under elongation.

The electrically conductive polymeric layers are resistant to temperatures in general, it can, if necessary, temperature resistance of> 100 ° C, in particular to about 200 0 C, to be achieved.

The inventive electrically conductive polymer layers have a transparency of> 80% a selective reflection may, if desired, be achieved, or, depending on the polymer produced or the mixture produced can be adjusted.

The electrically conductive polymers can also be pigmented with all the known pigments are suitable, the transparency is not to be significantly affected, however, are highly opaque or coloring pigments such as graphite, TiO 2 or carbon black is not suitable.

The proportion of pigments in the solid state can be up to 40%.

The adhesion of the polymer coating on the carrier substrate is generally very good, especially good adhesion when using polyethylenedioxythiophene - reached methanol by the higher polarity. The electrically conductive polymers can be present in both uniformly and partially on the support material.

The application of electrically conductive polymers according to one of the described Ausfϋhrungsformen of the process in the form of characters and patterns, area or line-shaped, wave-shaped or zigzag-shaped and similar or analogous structures, such as guilloches, carried longitudinally and / or cross-machine direction of the substrate. Further, the conductive polymers can also form recesses in the form of characters, patterns, flat, linear, wave-like, zigzag-shaped structures and / or guilloches on the substrate.

Linear or analogous structures have a directed in a preferential direction according to the orientation of the structures conductivity. Moreover, these structures provide additional security against destruction by transverse cracks in this and possibly overlying and / or underlying layer, as these are prevented from the interstices of the tear propagation. If such an electrically conductive layer protected by an additional layer, for instance a lacquer layer, or by laminating, the interstices or recesses ensure improved Versieglung the conductive polymer layer.

These structures provide, where appropriate, is also a two-dimensional coding.

Since the electrically conductive polymeric layers are mechanically and thermally highly resistant, but may be sensitive to moisture if necessary, these layers preferably do not lie directly on the surface of the substrate.

In one embodiment, for example, line- wavy or zigzag-shaped structures or guilloches to increase the conductor cross-section through cross-connections, which may have different widths or shapes and may optionally be arranged at different angles to the basic structure, can be connected.

The widths of the lines, waves or zigzag-shaped structures or guilloches, for example, 0.05 to 10 mm, preferably 0,1 - 0,3 mm, that of the cross-connections from 0.5 to 100 mm, preferably 1 to 10 mm.

The application of the electrically conductive monomers or polymers can take place in any known conventional manner, for example by spin coating, brushing, vapor deposition, by printing (gravure printing, flexographic printing, screen printing, offset printing, digital printing and the like) by spraying, sputtering, or roll coating techniques.

For the partial application of a soluble in a solvent ink or a soluble coating on the carrier substrate or possible can already be applied layers thereon. Subsequently, the conductive polymer is applied to this layer, whereupon the soluble ink is removed in the uncoated areas with the aid of the suitable solvent, optionally with mechanical support. However, it is also possible first, a corresponding coupling agents are partially applied in the desired form to the carrier substrate, then the electrically conductive polymer is applied over the entire surface, whereupon the polymer in those areas where no adhesive is present, by means of appropriate measures on the base adhesion the electrically conductive polymer are matched, can be detached again.

Furthermore, the partial application can also be made by the process described in DE 100 25 522 A1 method.

but the electrically conductive polymer layer can also be set adhesive or release capable.

To increase the conductivity, it is also possible to initially apply a layer of the electrically conductive polymer and then to apply a further layer of electrically conductive polymer for example by in-situ polymerization. Furthermore electrically conductive polymer layers of the invention may be particularly advantageously applied also in connection with an inorganic preferably metallic or pigmented layer. In this occurs not only an improvement in the electrical conductive properties of the coated substrate but also an additional assurance of proper functioning and identifiability.

Due to the improved extensibility of the electrically conductive polymers may malfunctions that may occur due to fine and very fine cracks in the inorganic conductive layer are bridged by the electrically conductive polymer layer.

A multi-layer structure of a full-area or partial layer of a conductive polymer having about the printed line-shaped, wave-shaped, and the like structures of the same polymer leads to different conductivities in different directions, for example parallel or transverse to the machine direction, but also at any angle to the machine direction.

If full-surface conductive polymeric base layer, for example, performed by a corresponding variable depth gravure cylinder in different thickness, while angle-dependent conductivities are achieved.

The polymeric conductive base layer and the second applied over polymeric conductive layer can also be separated by an insulator layer, if necessary.

However, it is also conceivable structures of more than 2 each full-area and / or partial electrically conductive polymeric layers, if necessary by insulating layer (s) may be separated.

is preferably / are not electrically conductive (n) (polymer (s)) layer (s) in direct contact with the metallic layers and is (are) separated from these by an insulator layer.

Further, the electrically conductive polymer layers, and also optionally encodes the additional inorganic metallic and / or pigmented electrically conductive layers as patches and thus also applied in machine-readable and / or structured. Further, the electrically conductive polymer layers can then be inline or offline embossed, perforated or micro-perforated.

The supporting substrate may already have functional or decorative layers, or it may be applied after application of the conductive layer, further layers. The substrates may additionally have a varnish layer, which unstructured or structured, for example, may be embossed. The varnish layer may for example be a release-capable transfer varnish layer, it may by radiation, for example, be cross-linked or cross-linkable UV radiation and be scratch-resistant and / or antistatic. Suitable are both aqueous and solid varnish systems, in particular varnish systems based on polyester-acrylate or epoxy acrylate, rosin, acrylate, alkyd, melamine, PVA, PVC, isocyanate, urethane systems, the conventional and / or reactive curing and may be / or radiation curing.

As dyes or lacquer layers variety of compositions may be used in each case. The composition of the individual layers may vary, so that the individual layers are exclusively decoration purposes or are to be a functional layer or whether the layer is a Dekorations¬ ais also to be both a functional layer, in particular after their task.

These layers can be pigmented or non-pigmented. As pigments, all known pigments, such as titanium dioxide, zinc sulphide, kaolin, ITO, ATO, FTO, aluminum, chromium and silicon oxides as well as colored pigments can be used. Solvent-borne coating systems as well as systems without solvents are used.

As the binder, various natural or synthetic binders are suitable.

The functional layers may comprise, for example, certain magnetic, chemical, physical and optical properties.

For adjusting the magnetic properties paramagnetic, diamagnetic and ferromagnetic materials such as iron, nickel and cobalt or their compounds or salts may be used (for example, oxides or sulfides).

Particularly suitable for use in conjunction with the present invention electrically conductive polymer layers are magnetic pigment inks with pigments based on Fe oxides, iron, nickel, cobalt and alloys thereof, barium or cobalt-ferrites, hard and soft magnetic iron and steel grades in aqueous or solvent-containing dispersions. As the solvent, for example, i-propanol, ethyl acetate, methyl ethyl ketone, Methoxypropano come! and their mixtures.

Preferably, the pigments are 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 placed in solvent-containing such dispersions.

The optical properties of the layer can be by visible dyestuffs or pigments, luminescent dyestuffs or pigments which fluoresce in the visible, in the UV range or in the IR range or phosphoresce, effect pigments such as liquid crystals, pearl luster, bronzes and / or multilayer - affect color change pigments and heat-sensitive inks or pigments. These can be used in all possible combinations. In addition, phosphorescent pigments can be used alone or in combination with other dyes and / or pigments.

It can also be combined various properties by adding various above-mentioned additives. So it is possible stained and / or use conductive magnetic pigments. All the abovementioned conductive additives are used.

Especially for staining of magnetic pigments are all known soluble and insoluble dyestuffs or pigments can be used. So a brown magnetic color by adding metals in their color, for example, for example, metallic, silvery be set.

For printing soluble layers also for applying partial inventive conductive layers, the color used or the color varnish used in a solvent, preferably soluble in water, but it may also be used an in any solvent, for example in alcohol, esters and the like soluble paint become. The color or the color varnish can be conventional compositions based on natural or artificial macromolecules. The color can be pigmented or non-pigmented. As pigments all known pigments can be used. Particularly suitable are TiO 2, ZnS, kaolin and the like.

When using a soluble ink layer where appropriate, may, after application of a further layer in the inventive method by a suitable solvent, which is matched to the composition of the color layer to be removed to be able to produce codings in the form of characters and / or patterns of any kind possible. Subsequently, the color layer is formed by a suitable solvent, which is matched to the composition of the color layer is removed. Preferably, the color application is water soluble. Optionally, the separation may be assisted by mechanical action.

Further, for example, insulating layers can be applied. As insulators are for example organic substances and their derivatives and compounds, for example paint and coating systems, such as epoxy, polyester, rosin, acrylate, alkyd, melamine, PVA, PVC, isocyanate, urethane systems, the radiation-curing can be suitable for example, by thermal or UV radiation.

Such layers can be used particularly in the production of multilayer structures, such as printed circuit boards between 2 or more electrically conductive polymer layers and / or electrically conductive metallic and / or pigmented layers that need to be separated from each other.

These layers can be applied by known methods, for example by vapor deposition, sputtering, printing (e.g., gravure, flexo, screen, offset, digital printing and the like), spraying, electroplating and the like. The thickness of the functional layers is generally from about 0.001 to 50 microns, preferably 0.1 to 20 microns.

Furthermore, partial or all-over metallic layers may be present or subsequently deposited on the carrier substrate. This layer consists of a metal, a metal compound or an alloy in which these metal layers may also represent inorganic electrically conductive layers. As the metal film layers consisting of Al, Cu, Fe, Ag, Au, Cr, Ni, Zn and the like suitable. Suitable metal compounds include oxides or sulfides of metals, in particular TiO 2, Cr oxides, ZnS, ITO, ATO, FTO, ZnO, Al 2 O 3 or silicon oxides suitable. Suitable alloys are, for example, Cu-Al alloys, Cu-Zn alloys and the like.

All these layers can be optionally also at least partially overlapping applied in a known manner, for example in a Metallsierungs- or demetallization, by printing and the like with the already existing layers both uniformly even partially passer- and accurate register.

The product is optionally therefore suitable, after appropriate assembly as a security element in data carriers, in particular valuable documents such as identity cards, cards, banknotes or labels, seals and the like, but also as a packaging material, for example in the pharmaceutical and food industries, for example in the form of blister films, folding boxes, covers, film packs and the like. Especially suitable are such products for applications in the electronics industry, for example, as circuit boards, RF antennas for transponders, and the like, displays, flexible circuits, medical equipment, electrode constructions, as heatable films, for example for windscreens, as a transparent reflective layer under holograms and / or structured layers and the like. Furthermore, they can, because of their excellent optical properties, be used as a "high refractive index" layer, as decorative or optical elements, for example in architecture and the like., The substrates or film materials are preferred for the application as security features cut into strips and threads wherein the width of the strips or threads preferably 0.05 - may be 10 mm.

Examples:

Example 1 :

A carrier film of PET having a thickness of 50 microns, which is already partially coated with an optically active layer and on which a commercially available

Adhesion promoter (A 1120, Fa. OSI) is applied is a mixture of Ethylendioxythiophenmethanol and iron (III) -toluenesulfonate and polyvinyl alcohol applied from a storage vessel via a transfer roll in the ratio 1:10:10 and polymerized in situ at 120 0 C and in situ washed

The film thus produced has a conductivity of 800Ω / square, the conductive layer has a transparency of 62% to.

The layer is to adhesive tape 100% and 40% elasticity, and thus suitable for deep drawing with little loss of conductivity.

In addition to the conductivity of the layer reflects 30% of the irradiated IR

Intensity in the near-IR and shows such an additional machine-readable

Property.

Example 2:

A carrier film of PET having a thickness of 50 microns, which is already partially coated with an optically active layer and on which a commercially available

Adhesion promoter (A 1120, Fa. OSI) is applied is from a storage vessel via a transfer roller, a mixture of 4-Metyhl-3-Oktoxythiophen and

Iron (III) -toluenesulfonate in the ratio 1: 10aufgebracht and polymerized in situ at 120 0 C and washed in situ.

The film thus produced has a conductivity of 1500Ω / square. The

Layer has a violet color.

When heated to about 100 0 C, the layer exhibits a color change from purple non-fluorescent to fluorescent yellow. Example 3:

The film produced according to Example 1 with a 10 micron PET - film with a 0.5 micron partial layer consisting θ of magnetic ink on the basis of Fβ 3 4 in an acrylate polymer dispersion and a 0.2 micron layer of a fluorescent ink laminated using a commercial laminating adhesive.

Subsequently, the surfaces have been provided with a heat seal lacquer.

The conductivity was 215 Ω / square, the magnetic properties were determined by 330 nW / m at a Koerzitivät of 250 oersteds.

Example 4:

In Fig. 6 a erfindungemäßes substrate with several additional functional characteristics is shown.

In this formula 1, a transparent flexible carrier substrate, 2 a coating with fluorescent properties, 4 an adhesive layer 5, the structured polymeric conductive layer, and 6 is a protective lacquer or an adhesive layer, for example a heat seal adhesive layer, 7 a Kaschierklebeschicht and 8, an opaque layer with recesses.

Claims

claims:
1) substrates with at least one electrically conductive layer, characterized in that the electrically conducting layer (s) (s) derivatives of thiophene or a mixture of thiophene derivatives is (s) comprising at least one additional, physical, machined to the conductivity readable property has (s) and printability regardless of the line width with high edge sharpness is (are).
2) substrates according to claim 1, characterized in that the electrically conductive layer (s) of alkyl-urethane, sulfonic acid, ether, ester, Benzo and aza (poly) -thiophenen such as (poly) ethylendioxythiophen- methanol Benzoethylendioxythiophen; (Poly) -3-hexylthiophene; (Poly) - thieno (3,4-b) -1, 4-dioxin-2-methanol, 2,3-dihydro; or (poly) -2H-thieno (3,4-b) (1,4) dioxepin-3-d, 3,4-dihydro-; thiophene derivatives or mixtures of these polymers, or mixtures of these polymers with other poly- consists (s).
3) Substrates according to claim 1 or 2, characterized in that the layer (s) are available from electrically conductive polymers, partially or fully on the substrate.
4) substrates according to one of claims 1 to 4, characterized in that the layer (s) of electrically conductive polymers in the form of characters, patterns, flat, linear, wave-like, zigzag-shaped structures and / or guilloche patterns present on the substrate /are.
5) substrates according to one of claims 1 to 4, characterized in that the electrically conductive polymers form gaps in the form of characters, patterns, flat, linear, wave-like, zigzag-shaped structures and / or guilloches. 6) substrates according to one of claims 1 to 5, characterized in that the layer (s) of electrically conductive polymers in the form of linear, wave-like, zigzag-shaped structures and / or guilloche patterns having a directed in the preferred direction conductivity / have.
7) substrates according to claim 6, characterized in that the structures be longitudinally or transversely, or at any angle to the machine direction.
8) substrates according to one of claims 1 to 7, characterized in that the structures represent a 2-dimensional coding.
9) substrates according to one of claims 1 to 8, characterized in that the conductive layers do not lie on the surface of the substrates.
10) Substrates according to one of claims 1 to 9, characterized in that the electrically conductive polymer layers have a further machine-readable feature.
11) Substrates according to claim 10, characterized in that the electrically conductive polymer layer is IR-reflecting.
12) Substrates according to claim 10, characterized in that the electrically conductive polymer layer thermochromic properties.
13) Substrates according to claim 10, characterized in that the electrically conductive polymer layer electrochromic properties. 14) Substrates according to claim 10, characterized in that the electrically conductive polymer layer has a diffuse or shiny metallic VIS reflection.
15) Substrates according to one of claims 1 to 14, characterized in that the comprise the conductive polymer (s) layer (s) has a defined adjustable conductivity /.
16) Substrates according to one of claims 1 to 15 characterized in that the electrically conductive polymer (s) layer (s) have a defined color in correlation with the adjustable conductivity.
17) Substrates according to one of claims 1 to 16, characterized in that further ink, paint, metallic layers and / or surface structures are additionally present, in which metallic and conductive layers border directly or not directly to each other.
18) Substrates according to one of claims 1 to 17, characterized in that additional inorganic metallic and / or pigmented electrically conductive layers are applied.
19) Substrates according to one of claims 1 to 18, characterized in that the electrically conductive layer (s) (s) encoded as patches, are machine-readable and / or patterned applied.
20) Substrates according to one of claims 1 to 19, characterized in that the electrically conductive polymer layers subsequently inline or offline embossed, perforated, are micro perforated.
21) sheet material having at least one electrically conductive layer, characterized in that the electrically conducting layer (s) derivatives of thiophene or a mixture of thiophene derivatives is (s) having at least one additional, physical, machine readable to the conductivity property (s) and independent of the line width with high edge sharpness is printability (are).
22) Sheet material according to claim 21, characterized in that the electrically conductive layer (s) of alkyl-urethane, sulfonic acid, ether, ester, Benzo and aza (poly) -thiophenen such as (poly) ethylendioxythiophen- methanol Benzoethylendioxythiophen; (Poly) -3-hexylthiophene; (Poly) - thieno (3,4-b) -1, 4-dioxin-2-methanol, 2,3-dihydro; or (poly) -2H-thieno (3,4-bχi, 4) dioxepin-3-d, 3,4-dihydro-; thiophene derivatives or mixtures of these polymers, or mixtures of these polymers with other poly- consists (s).
23) Sheet material according to claim 22, characterized in that the layer (s) are available from electrically conductive polymers, partially or fully on the substrate.
24) Sheet material according to any one of claims 21 to 23, characterized in that the layer (s) of electrically conductive polymers in the form of characters, patterns, flat, linear, wave-like, zigzag-shaped structures and / or guilloche patterns present on the substrate /are.
25) Sheet material according to any one of claims 21 to 23, characterized in that the layer (s) form of electrically conductive polymers gaps in the form of characters, patterns, flat, linear, wave-like, zigzag-shaped structures and / or guilloches on the substrate ,
26) Sheet material according to any one of claims 21 to 25, characterized in that the layer (s) of electrically conductive polymers in the form of linear, wave-like, zigzag-shaped structures and / or guilloche patterns having a directed in the preferred direction conductivity / have.
27) Sheet material according to claim 26, characterized in that the structures be longitudinally or transversely, or at any angle to the machine direction.
21 to 27 characterized in 28) A sheet material according to any of claims, that the structures represent a 2-dimensional coding.
29) A sheet material according to any one of claims 21 to 28, characterized in that the conductive layers do not lie on the surface of the substrates.
30) A sheet material according to any one of claims 21 to 29, characterized in that the electrically conductive polymer layers have a further machine-readable feature.
31) Sheet material according to claim 30, characterized in that the electrically conductive polymer layer is IR-reflecting.
32) Sheet material according to claim 30, characterized in that the electrically conductive polymer layer thermochromic properties.
33) Sheet material according to claim 30, characterized in that the electrically conductive polymer layer electrochromic properties. 34) Sheet material 'according to claim 30, characterized in that the electrically conductive polymer layer has a diffuse or shiny metallic VIS reflection.
Characterized in 35) A sheet material according to any one of claims 21 to 34, the conductive polymer (s) layer (s) has a defined adjustable conductivity / have.
36) Sheet material according to any one of claims 21 to 35, characterized in that the electrically conductive polymer (s) layer (s) have a defined color in correlation with the adjustable conductivity.
37) Sheet material according to any one of claims 21 to 36, characterized in that further ink, paint, metallic layers and / or surface structures are additionally present, in which metallic and conductive layers do not directly adjoin one another.
38) Sheet material according to any one of claims 21 to 37, characterized in that additional inorganic metallic and / or pigmented electrically conductive layers are applied.
39) Sheet material according to any one of claims 22 to 38, characterized in that the electrically conductive layer (s) (s) encoded as patches, is machine-readable and / or patterned applied (are).
40) Sheet material according to any one of claims 20 to 39, characterized in that the electrically conductive polymer layers are then inline or embossed offline.
41) Security elements in the form of a thread, strip, ribbon, patches, or other format, in particular for at least partial embedding in or for application on security papers, documents of value, data carriers, banknotes, packaging, and the like, characterized in that it optionally off after assembly one of the substrates according to claims 1 - 20 or the sheet material according to claims 21 - were prepared 41st
42) security papers, documents of value, data carriers, banknotes, packaging materials, characterized in that they comprise at least one security element according to claim 41st
43) A process for the production of substrates with electrically conductive layers, characterized in that the monomer or prepolymer can be applied to the carrier substrate and is polymerized in situ.
44) The method according to claim 43, characterized in that, when the catalyst residues are removed in situ in situ polymerization.
45) A method according to any one of claims 43 or 44, characterized in that monomer to initiator and / or catalyst in a weight ratio of 1: are prepared or deposited 100: 5 to. 1
46) A method according to any one of claims 43 to 45, characterized in that used as monomer Baytron ® types and as an initiator and / or catalyst Baytron ® C types.
47) A method according to any one of claims 41-46, characterized in that an additional catalyst is used.
48) A method according to any one of claims 41-47, characterized in that the application of the monomer and the initiator and / or catalyst or monomer / initiator and / or catalyst mixture is temperature controlled.
49) A method according to any one of claims 41-48, characterized in that the initiator catalyst residues are removed and / or and / or other unwanted reaction products by washing with a suitable solvent.
50) The method according to claim 49, characterized in that initiator and / or catalyst residues and / or other unwanted reaction products by washing with by Umkehrosomose, ion exchangers, distillation and / or physical Aufbreitungsanlagen treated water with a defined content of alkali and / or alkaline earth metal ions are removed.
51) A method according to any one of claims 41- 50, characterized in that the water used for washing is recirculated and is by means of filtration, ion exchangers and / or distillation prepared.
52) Method according to one of claims 41 to 51, characterized in that, as required by Umkehrosomose, ion exchangers, distillation and / or physical Aufbreitungsanlagen treated fresh water is supplied to the washing water circuit.
53) Method according to one of claims 41 to 52, characterized in that a final washing step with by Umkehrosomose, ion exchangers, distillation and / or physical Aufbreitungsanlagen is performed treated fresh water.
54) A method according to any one of claims 41 - 53, characterized in that the washing-line or out of line is performed. 55) Method according to one of claims 41 to 54, characterized in that the already functional and / or decorative layers are present on the carrier substrate and / or subsequently applied.
56) Use of the substrates according to any one of claims 1 - 20 and / or Foüenmaterialien according to any one of claims 21-41, optionally after assembly as a security element in data carriers, in particular valuable documents such as identity cards, cards, banknotes or labels, seals, as packaging material in the pharmaceutical and food industries, for decorative applications or optical elements, in architecture, in the electronics industry as circuit boards, RF antennas for transponders, and the like, for displays, flexible circuits, medical equipment, electrode constructions, as heatable films, for example for windscreens, as a transparent reflective layers under holograms and / or structured layers, and as a high refractive index layer.
PCT/EP2004/011855 2004-10-20 2004-10-20 Substrates comprising electroconductive layers WO2006042568A1 (en)

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EP0426801B1 (en) 1989-05-12 1995-03-22 GAO Gesellschaft für Automation und Organisation mbH Security document with embedded security element with visually and mechanically verifiable distinguishing signs
EP0753623A2 (en) * 1995-07-14 1997-01-15 MANTEGAZZA ANTONIO ARTI GRAFICHE S.r.l. Security sheet, particularly of the type that includes an electrically conducting element
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WO2010097231A1 (en) * 2009-02-26 2010-09-02 Zyrus Beteiligungsgesellschaft Mbh & Co. Patente I Kg Apparatus and method for producing a conductive structured polymer film

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