EP1357226A2 - Substrates with electrically conducting layers - Google Patents

Abstract

A substrate or film carries a layer of an electrically-conductive polymer. Independent claims are also included for (1) production of a substrate carrying an electrically-conductive layer by in-situ polymerization of a monomer or pre-polymer or by application of a polymer dispersion; (2) apparatus for applying the polymer dispersion, the monomer solution or the monomer/initiator or catalyst mixture in a solvent, the apparatus comprising a temperature-controlled application tank, plunge cylinder, application roller or printer; and (3) a magnetic pigment composition for use with the electrically-conductive product, the composition comprising pigments based on iron oxide, iron, nickel-cobalt or alloys, barium, cobalt-ferrite or hard or soft magnetic iron or steel in aqueous, solvent-free or solvent-containing dispersions such as nitrocellulose, acrylate polymer dispersions of mol. wt. 150,000-300,000, acrylate-urethane dispersions or acrylate-styrene or PVC (co)polymer dispersions.

Description

The invention relates to substrates with electrically conductive layers, methods and a device for their production and their use.

In the production of coated substrates, conductive inks or lacquers are usually used for printing electrically conductive layers. The paints or varnishes are generally mixed with electrically conductive pigments, for example carbon black, graphite, silver and the like. However, the inks and varnishes with these pigments are clearly visible after printing, especially on transparent substrates.
In various applications, however, it is undesirable for the electrically conductive layers applied to be immediately recognizable. This applies in particular to the use in security features for data carriers, value documents and products of all kinds.

From EP 0 426 801 B, for example, security elements for security documents are known 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.

In particular for safety applications, however, are for a safe function and certain identifiability of the electrically conductive features To make demands on the electrically conductive layer, especially what electrical resistance, mechanical resistance, flexibility, the extensibility, the temperature and chemical resistance concerns with the known solutions can not be achieved satisfactorily. Especially when used as RF antennas for transponders, in Anti-theft labels, smart cards and the like must also be secure Function must be guaranteed.

The object of the invention is therefore to provide substrates with invisible, preferably transparent, electrically conductive layers that additionally have the desired properties mentioned above.

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.

Another object of the invention is a method for producing Substrates with at least one electrically conductive layer, thereby characterized in that a monomer or prepolymer on the carrier substrate is applied and polymerized in situ, the initiator and / or Catalyst and / or catalyst can also be removed in situ or the Polymers can be applied as a dispersion to the carrier substrate.

The electrically conductive polymers can be, for example, polyacetylene, poly-p-phenylene, Polypyrroles, polythiophenes, poly-p-phenylene vinylene, low molecular weight macrocyclic semiconductors, organopolysilanes, Be poly-sulfur nitride and / or polyanilines and / or their derivatives. Polyaniline or are particularly preferred as electrically conductive polymers Polyethylene dioxythiophene used.

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 include, for example, carrier films, preferably flexible transparent plastic films, for example made of PI, PP, MOPP, PE, PPS, PEEK, PEK, PEI, PAEK, LCP, PEN, PBT, PET, PA, PC, COC, POM, ABS, PVC in question.
The carrier films preferably have a thickness of 5 to 700 μm, preferably 5 to 200 μm, particularly preferably 15 to 50 μm.

Furthermore, metal foils, for example Al, Cu, Sn, Ni, Fe or stainless steel foils with a thickness of 5 - 200 µm, serve preferably 10 to 80 microns, particularly preferably 20 - 50 microns. The Films can also be surface-treated, coated or laminated for example with plastics or painted.

Further, as 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.

Furthermore, 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.

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). In 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, in Fig. 4 a scheme for the preparation of the washing liquid and in 5 and 5a an embodiment of the invention Application device with storage container and separate also as Dosing units provided storage containers.

1 to 3, 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.
In FIG. 4, 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.

5 and 5a show a preferred application device (2 or 2b, and 3 as shown in FIGS. 1-3) with the associated additional immersion cylinder 3a described in more detail below. In the preferred application device, 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. 25 denotes a distributor tunnel for the monomer / initiator and / or catalyst and / or catalyst mixture, 26 the distributor plate of the distributor tunnel.
In FIG. 5a, 27 means the storage container for the monomer and 28 the storage container for the initiator and / or catalyst and 29 the storage container for the solvent.

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). Examples of suitable dispersants are inert solvents, preferably aqueous solvents or alcohols, such as i-propanol. Optionally, 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.
For example, 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.

It is preferably from a storage container as shown in 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. In the inner tub Dispersion via a distributor tunnel 25 and the distributor plate 26, the with regularly arranged openings is provided, evenly distributed.

The filter prevents polymer particles from agglomerating be applied. The mesh size of the filter is determined accordingly according to the particle size of the polymer in the dispersion. Be at the same time possible impurities are also retained.

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. Depending on the amount of filling in the 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 immersion cylinder now takes the polymer dispersion out of the inner tub and transfers them to the transfer cylinder. The excess runs now Dispersion that is not absorbed by the transfer cylinder over the Outside of the inner tub back into the outer tub 21. The same goes for that Polymer dispersion portion that is not on the doctor blade 4 (not shown in Figure 5) was applied to the application tool, back into the outer tub.

Due to the orientation of the outer tub not flat on one level, but with a slight slope from the side of the drain facing away from the drain Paint tray to the side on which the drain is located, the in the Outside tub 21 collected dispersion from the whole Paint application unit guided back into the reservoir 23a. In the The inner tub is therefore always only from the storage container below defined temperature and with that defined by the pump 23 b Inflow rate introduced polymer dispersion.

By avoiding the return of not over the following cylinders and the doctor blade applied polymer dispersion in the inner tub becomes the The temperature of the polymer dispersion in the inner tub was kept correctly constant air intake also avoided. Furthermore, the temperature of the polymer dispersion in the inner tub constantly via a temperature sensor (not in Fig. 5 shown) can be checked.

Then the applied dispersion is dried by the Drying devices 5 or the washing process in the washing station 6 for Removal of solvent residues (Fig.1)

However, the monomers or prepolymers for forming the electrically conductive polymers are preferably applied and polymerized in situ (FIGS. 2, 3 and 5a).
Both radical and redox or photo-initiator and / or catalysts and / or catalysts, for example UV, can be used as initiators and / or catalysts.

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

Optionally, a catalyst to accelerate the Reaction can be added, for example a Ziegler-Natta catalyst, or a Pt catalyst, in which case the amount of Initiator and / or catalyst can be lower.

In one embodiment, as shown in Figure 2, 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. After the polymerization, 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)

In the particularly preferred embodiment, 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 preferred embodiment of the application device, as shown in FIG. 5a, has, in addition to the elements shown in FIG. 5, a storage container for the monomer and a separate storage container for the initiator and / or catalyst or the initiator and / or catalyst or additional Catalyst mixture and for any additional solvent to be metered in. The solvent is preferably metered in via a viscosity regulator.
It is also possible to provide a solution of monomer or prepolymer and initiator and / or catalyst in one storage container and the solvent to be metered in, if appropriate, in a second storage container.

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

If 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).

To avoid possible dangerous residues in the conductive layer 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.

In the process according to the invention, the pure substances (monomer, Initiator and / or catalyst) without the addition of further binders and / or Additives used.

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. To 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. Preferably the unwanted polymerization but by metering in the solvent controlled diluted monomer present

Alternatively, 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.

In a commissioned work designed in accordance with FIGS. 5 and 5a therefore by adjusting the ratios of the mixture components or Temperature controlled the reaction kinetics and at the same time a more uniform homogeneous application of the polymer dispersion or the monomer solution or the Monomer / initiator and / or catalyst mixture reached.

Depending on the solvent used, 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.

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. By adding the ions present in the water to the O atoms of the ethylenedioxythiophene units, complexes are formed, which changes the configuration of the macromolecules and thus shifts the band gap in the absorption spectrum and thus the absorption maximum.
At the same time, this complex formation also changes the conductivity and can therefore be defined in a defined manner by the ion content in the water.

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 .

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. With Initiator or initiator and catalyst saturated wastewater is over a Filter system and then via ion exchanger and / or through Prepared distillation. To ensure continuous operation, 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.

If necessary, a washing process with pure, as above treated, fresh water.

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 µm, preferably 0.5-10 µm. For certain uses are thinner layers of 0.001 - 50 µm, preferably 0.05 - 10 µm easily producible.

Furthermore, 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.

With the electrically conductive polymer layers according to the invention if desired, a transparency of> 80% 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%.

If necessary, 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.

The application of the electrically conductive polymers according to one of the described embodiments of the method in the form of characters and Patterns, flat or linear, wavy or zigzag and similar or analog structures, such as guilloches, lengthways and / or transversely to the machine direction of the substrate.

Linear or analog structures have a conductivity directed in a preferred direction in accordance with the orientation of the structures. In addition, 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.

Since 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.

In one embodiment, for example, line waves or zigzag structures or guilloches to increase the Line cross-section over cross-connections, 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.

For partial application, 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.

However, 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.

Furthermore, the partial application can also be carried out in accordance with DE 100 25 522 A1 described procedures take place.

The electrically conductive polymer layer can also be adhesive or can be set for release.

In order to increase the conductivity, it is also possible to first coat one layer apply the electrically conductive polymer and then another Layer of the electrically conductive polymer, for example, by in-situ To apply polymerization. Furthermore, 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.

Due to the better stretchability of the electrically conductive polymers, Malfunctions caused by fine and very fine cracks in the inorganic conductive layer can occur through the electrically conductive Polymer layer can be bridged.

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.

For example, 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.

But there are also structures made up of more than 2 full-surface and / or partial polymeric electrically conductive layers that may be caused by Insulator layer (en9 can 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.

Furthermore, 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.

A wide variety of different layers of paint or varnish can be used 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. As 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. There are solvent-based paint systems as Systems without solvents can also be used.

Various natural or synthetic binders come as binders in question.

The functional layers, for example, can have certain magnetic, have chemical, physical and optical properties.

To set the magnetic 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. Examples of suitable 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. In addition, phosphorescent pigments can also be used alone or in Combination with other dyes and / or pigments can be used.

You can also add different properties by adding different ones above additives can be combined. So it is possible stained and / or to use conductive magnetic pigments. All are mentioned conductive additives can be used.

All known ones can be used especially for coloring magnetic pigments Use soluble and insoluble dyes or pigments. So can for example a brown magnetic paint by adding metals to it Metallic color, e.g. silvery.

For printing soluble layers, also for applying partial conductive layers according to the invention, 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.

If 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.

To further improve the dissolving of the covered color layer, too a thin, highly pigmented layer of paint over the entire surface or in register and / or a pure pigment layer are applied, the thickness of this Layer is about 0.01 - 5 microns.

Insulator layers can also be applied, for example. Examples of 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.

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

Furthermore, 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. Examples of 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.

If highly pigmented systems are applied using the gravure printing process, undesirable toning residues form on the film, in particular depending on the doctor blade used, ie thin layers are applied to the film outside the printing areas. As a result, the adhesion of the layers subsequently applied can be impaired.
In order to avoid the formation of such toning residues on the film, in addition to the optimization of the doctor blade and cylinder roughness, systems can also be used which largely dry these thin layers on the cylinder surface and thus prevent transmission to the film.
For example, a blow bar with several nozzles arranged over the entire width can be located between the doctor blade and the pressure roller. Through these nozzles, filtered air with defined air humidity, possibly heated or cooled, 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.
Instead of such a blow molding, an IR drying device situated over the entire width can also be used.

However, 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, if appropriate, is particularly advantageous when applying metallic layers.
At the same time, the surface is activated. Terminal polar groups are created on the surface. This improves the adhesion of metals and the like to the surface.

If necessary, 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.

As a result, the liability of another is partially or fully applied structured functional layer further improved. That is a requirement for the production of functional layers with high precision and good Liability.

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. Further Because of their excellent optical properties, they can be called "high refractive index "layer, as decorative or optical elements, for example used in architecture and the like. For use as Security features are preferred in Stripes and threads cut, the width of the stripes or threads can preferably be 0.05-10 mm.

Examples: Example 1:

On a carrier film made of PET with a thickness of 50 µm, which is already partially an optically active layer is coated, and on which a commercially available Adhesion promoter (A 1120, OSI)) is applied from a storage container 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 µm applied. Then the applied polymer layer at 110 ° C. dried.

The film thus produced has a conductivity of 800Ω / square conductive layer has a transparency of 87%

Example 2:

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 Ω / square and the two conductive layers together have a transparency of 82% on.

One subsequently partially applied to the film in a known manner fluorescent paint layer shows no influence on the conductivity or Transparency of the free areas of the conductive layers.

Example 3:

Analogously to Example 1, 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 μm 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 Ω / square.

Example 4:

The film produced according to Example 3 is coated with a 10 μm PET film with a 0.5 μm partial layer consisting of a magnetic printing ink based on Fe ₃ O ₄ in an acrylate polymer dispersion and a 0.2 μm layer made of a fluorescent printing ink laminated using a standard laminating adhesive.

The surfaces were then coated with a heat seal lacquer.

The conductivity was 215 Ω / square, the magnetic properties were determined with 330 nW / m at a coercivity of 250 Oerstedt.

Claims (58)

Substrates with at least one electrically conductive layer, characterized in that the electrically conductive layer consists of conductive polymers. Substrates according to claim 1, characterized in that the layer (s) made of electrically conductive polymers are partially or completely present on the substrate. Substrates according to one of claims 1 or 2, characterized in that the layer (s) made of electrically conductive polymers is / are present on the substrate in the form of characters, patterns, flat, linear, wavy, zigzag structures and / or guilloches , Substrates according to one of claims 1 to 3, characterized in that the layer (s) made of electrically conductive polymers in the form of line, wave, zigzag structures and / or guilloches has / have a conductivity directed in the preferred direction. Substrates according to claim 4, characterized in that the structures are present lengthways or crossways or at any angle to the machine direction. Substrates according to one of claims 1 to 5, characterized in that the structures represent a 2-dimensional coding. Substrates according to one of claims 1 to 6, characterized in that the conductive layers are not on the surface of the substrates. Substrates according to one of claims 1 to 7, characterized in that the electrically conductive polymers are polyacetylene, poly-p-phenylene, polypyrroles, polythiophenes, poly-p-phenylene vinylene, low molecular weight macrocyclic semiconductors, organopolysilanes, poly-sulfur nitride and / or polyanilines and / or their Derivatives are used. Substrates according to claim 7, characterized in that polyaniline or polyethylene dioxythiophene is used as the electrically conductive polymer. Substrates according to claim 8, characterized in that the electrically conductive polymer used is polyethylene dioxythiophene in a matrix polymer. Substrates according to one of Claims 1 to 10, characterized in that that as an electrically conductive polymer, polyethylene dioxythiophene (PEDT), which is stabilized via a non-polymer-bound anion, is used. Substrates according to claim 11, characterized in that the electrically conductive polymer used is polyethylene dioxythiophene toluenesulfonate (PEDT / TS, P-DOT). Substrates according to one of claims 1 to 12, characterized in that the electrically conductive polymer layers have a transparency of> 80%. Substrates according to one of claims 1 to 13, characterized in that the conductive polymer layer (s) has / have a defined adjustable conductivity. Substrates according to one of claims 1 to 14, characterized in that the electrically conductive (n) polymer layer (s) have a defined color in correlation to the adjustable conductivity. Substrates according to one of claims 1 to 15, characterized in that additional color, lacquer, metallic layers and / or surface structures are additionally present, metallic and conductive layers not directly adjoining one another. Substrates according to one of claims 1 to 14, characterized in that additional inorganic metallic and / or pigmented electrically conductive layers are applied. Substrates according to one of claims 1 to 15, characterized in that the electrically conductive layer (s) are encoded as patches, machine-readable and / or applied in a structured manner. Substrates according to one of claims 1 to 16, characterized in that the electrically conductive polymer layers are subsequently embossed inline or offline. Foil material with at least one electrically conductive layer, characterized in that the electrically conductive layer consists of conductive polymers. Foil material according to claim 20, characterized in that the layer (s) made of electrically conductive polymers are partially or completely present on the substrate. Foil material according to one of claims 20 or 21, characterized in that the layer (s) made of electrically conductive polymers is / are present on the substrate in the form of characters, patterns, flat, linear, wavy, zigzag structures and / or guilloches , Foil material according to one of claims 20-22, characterized in that the layer (s) made of electrically conductive polymers in the form of line, wave, zigzag structures and / or guilloches has / have a conductivity directed in the preferred direction. Substrates according to claim 23, characterized in that the structures are present lengthways or crossways or at any angle to the machine direction. Foil material according to one of claims 18 to 24, characterized in that the structures represent a 2-dimensional coding. Foil material according to one of claims 20 to 25, characterized in that the conductive layers are not on the surface of the substrates. Foil material according to one of claims 20 to 26, characterized in that the electrically conductive polymers are polyacetylene, poly-p-phenylene, polypyrroles, polythiophenes, poly-p-phenylene vinylene, low molecular weight macrocyclic semiconductors, organopolysilanes, poly-sulfur nitride and / or polyanilines and / or their Derivatives are used. Foil material according to claim 27, characterized in that polyaniline or polyethylene dioxythiophene is used as the electrically conductive polymer. Foil material according to claim 28, characterized in that the electrically conductive polymer used is polyethylene dioxythiophene in a matrix polymer. Foil material according to one of claims 20 to 29, characterized marked that as an electrically conductive polymer Polyethylene dioxythiophene (PEDT), which is a non-polymer bound anion is stabilized, is used Foil material according to claim 30, characterized in that the electrically conductive polymer used is polyethylene dioxythiophene / toluenesulfonate (PEDT / TS; P-DOT). Foil material according to one of claims 20 to 31, characterized in that the electrically conductive polymer layers have a transparency of> 80%. Foil material according to one of claims 20 to 32, characterized in that the conductive polymer layer (s) has / have a defined adjustable conductivity. Foil material according to one of claims 20 to 33, characterized in that the electrically conductive polymer layer (s) have a defined coloration in correlation to the adjustable conductivity. Foil material according to one of claims 20 to 34, characterized in that additional color, lacquer, metallic layers and / or surface structures are additionally present. Foil material according to one of claims 20 to 36, characterized in that additional inorganic metallic and / or pigmented electrically conductive layers are applied. Foil material according to one of claims 20 to 37, characterized in that the electrically conductive layer (s) are encoded as patches, machine-readable and / or applied in a structured manner. Foil material according to one of claims 20 to 38, characterized in that the electrically conductive polymer layers are subsequently embossed inline or offline. Security elements in the form of a thread, strip, tape, patches or other format, in particular for at least partial embedding in or for application to security papers, value documents, data carriers, banknotes, packaging, and the like, characterized in that , if required, they are made up from one of the Substrates according to claims 1-19 or the film material according to claims 20-38 were produced. Security papers, documents of value, data carriers, banknotes, packaging materials, packaging, characterized in that they have at least one security element according to claim 39. Process for the production of substrates with electrically conductive layers, characterized in that the monomers or prepolymers are applied to the carrier substrate and polymerized in situ or the polymers are applied as a dispersion to the carrier substrate. A method according to claim 37, characterized in that catalyst residues are removed in situ in the in situ polymerization. Method according to one of claims 37 or 38, characterized in that monomer to initiator and / or catalyst are introduced or applied in a weight ratio of 1:20 to 1: 100. A method according to claim 39, characterized in that monomer to initiator and / or catalyst are introduced or applied in a weight ratio of 1:50 to 1:80. Method according to one of claims 37 to 40, characterized in that Baytron® M types are used as the monomer and Baytron® C types are used as the initiator and / or catalyst. Method according to one of claims 37-41, characterized in that a catalyst is additionally used. Method according to one of claims 37- 42, characterized in that the application of the polymer dispersion, the monomer and the initiator and / or catalyst or the monomer / initiator and / or catalyst mixture is carried out in a temperature-controlled manner. Method according to one of claims 37 - 43, characterized in that initiator and / or catalyst residues and / or other undesirable reaction products are removed by washing with a suitable solvent. A method according to claim 44, characterized in that initiator and / or catalyst residues and / or other undesirable reaction products by washing with water treated by reverse osmosis, ion exchangers, distillation and / or physical treatment plants with a defined content of alkali and / or alkaline earth ions removed become. Method according to one of claims 37- 45, characterized in that the water used for washing is circulated and processed by means of filtration, ion exchanger and / or distillation. Method according to one of claims 45 or 46, characterized in that fresh water prepared by reverse osmosis, ion exchanger, distillation and / or physical treatment plants is fed to the wash water circuit as required. Method according to one of claims 37-47, characterized in that a final washing step is carried out with fresh water treated by reverse osmosis, ion exchange, distillation and / or physical treatment plants. Method according to one of claims 37-48, characterized in that the washing process is carried out inline or out of line. Method according to one of claims 37 to 49, characterized in that functional and / or decorative layers are already present on the carrier substrate and / or are subsequently applied. Device for applying the polymer dispersion, the monomer solution and / or the monomer / initiator or / and / or catalyst mixture in a solvent, characterized in that the application unit consists of a temperature-controlled application pan, a temperature-controlled immersion cylinder, a temperature-controlled transfer roller and a temperature-controlled pressure tool consists. Apparatus according to claim 46, characterized in that the temperature-controlled storage container (2) consists of an inner and an outer trough, the inner trough having an inner surface essentially in the form of a half-cylinder with a return plate which continues this shape on one side and which is at least up to half extends to 2/3 of the circumference of the immersion cylinder engaging in the inner tub and the outer tub is arranged inclined in the direction of the side facing away from the drain towards that side of the side facing the drain. Use of the substrates according to one of claims 1-19 and / or film materials according to one of claims 20-38 if necessary after assembly as a security element in Data carriers, especially documents of value such as ID 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 printed circuit boards, RF antennas for transponders and the like, for displays, flexible circuits, medical Devices, electrode structures, as heatable films, for example for windscreens, as transparent reflective layers under Holograms and / or structured layers, and as high refractive index layer. Magnetic pigment paint for use in conjunction with electrical conductive polymer layers in one of the substrates according to one of the Claims 1- 19 or one of the film materials according to one of the Claims 20 - 38, consisting of pigments based on Fe oxides, Iron, nickel cobalt and their alloys, barium or cobalt ferrite, hard and soft magnetic types of iron and steel in aqueous, solvent-free or solvent-containing dispersions such as Nitrocellulose, acrylic polymer dispersions with a molecular weight from 150,000 to 300,000, in acrylate urethane dispersions, acrylate styrene or PVC-containing and their copolymers dispersions.

Images