WO2006042568A1

WO2006042568A1 - Substrates comprising electroconductive layers

Info

Publication number: WO2006042568A1
Application number: PCT/EP2004/011855
Authority: WO
Inventors: Friedrich Kastner; Martin Bergsmann; Evelyne Wagner
Original assignee: Hueck Folien Ges.M.B.H
Priority date: 2004-10-20
Filing date: 2004-10-20
Publication date: 2006-04-27
Also published as: EP1805033A1

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, methods and apparatus for their preparation and their use.

In the production of coated substrates, conductive paints or lacquers are usually used for printing electrically conductive layers. In general, electrically conductive pigments, for example carbon black, graphite, silver and the like, are added to the paints or lacquers. However, the paints and varnishes 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 applies in particular to the use in security features for data carriers, value documents and products of all kinds.

For example, EP 0 426 801 B discloses security elements for security documents which have characters which are hidden in incident light, can be seen in transmitted light and which are also designed to be electrically conductive, wherein the electrically conductive material is present over at least one surface of the security element and is made transparent or semi-transparent at least in some areas and is arranged above and / or below the characters. The electrically conductive material is always located on the surface of the security feature. In this case, the transparent or semitransparent material is realized either by an indium tin oxide layer or by sputtering a metal layer, in particular an aluminum layer.

However, in particular for security applications, certain requirements are to be placed on the electrically conductive layer, in particular for a reliable function and identifiability of the electrically conductive features the electrical resistance, the mechanical resistance, the flexibility, the ductility, the temperature and chemical resistance, which can not be satisfactorily achieved with the known solutions. In particular, when used as RF antennas for transponders, in anti-theft labels, smart cards and the like, a secure function must be ensured.

From EP 1 185 422 B1, an optically variable security feature with diffractive structures is known, consisting of an electrically conductive polymer and at least one carrier film, a protective layer, a lacquer layer and a reflection layer, wherein the electrically conductive polymer is a polyethylenedioxythiophene-polystyrenesulfonate arranged at different layers is.

From WO 99/66128 electrical feature substances for integration into pulp webs are known, with polyethylenedioxythiophene-polystyrenesulfonate being used as the electrically conductive, transparent polymer.

However, the available formulations of polyethylene dioxythiophene in the matrix polymer polystyrenesulfonate have only defined viscosities, which can not be changed in the application, without serious disadvantages in the processing and application of the polymer or negative influences on the quality of the coating to accept. However, the change or adjustment of a defined viscosity is of crucial importance especially in the partial application of the conductive polymer. Depending on the print motif, desired layer thickness, conductivity and transparency, a different viscosity leads to the optimum result. For example, For printing fine rasters, ie fine structures in the printed image, low viscosities are required in order to obtain exact contours and edges.

Polyethylene dioxythiophene is also known by printing in-situ polymerization of the monomer, for example Baytron M with a Catalyst, for example, Fe (lll) toluenesulfonate applied by printing technology. Also in this method, the setting of a defined viscosity to achieve a print image with high edge sharpness is hardly possible because it serious disadvantages in the in situ polymerization (insufficient polymerization and therefore low conductivity and significant coloration of the layer) must be taken into account.

Furthermore, it is desirable that security features in addition to the conductivity of an additional, preferably machine readable property to ensure increased security against counterfeiting. The currently known and used electrically conductive polymers are usually transparent, but have no additional property apart from the conductivity per se, which would meet these requirements. Additional, preferably machine-readable properties can currently only be achieved by suitable additives (for example dyes and the like).

The object of the invention is therefore the provision of substrates with electrically conductive polymeric layers, which additionally have the above-mentioned desired properties, namely an additional machine-readable feature and high edge sharpness of the printed image regardless of the line width.

The invention therefore substrates with at least one electrically conductive layer, characterized in that the electrically conductive (s) layer (s) of thiophene derivatives or a mixture of thiophene derivatives (s), the at least one additional to the conductivity, has physical, machine readable property (s) and is printable with high edge sharpness regardless of line width (are).

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

Suitable poly-thiophene derivatives are alkyl, urethane, sulfonic acid, ether, ester, benzo and aza- (poly) thiophenes, for example polymers of the monomers or ethylenedioxythiophenemethanol; 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-.

In addition to the conductivity, these polymeric conductive coatings each have an additional visually recognizable or machine-readable property.

For example, the polyethylenedioxythiophenemethanol prepared in situ exhibits IR-reflecting properties,

Polythiophene thermally induced thermochromic and fluorescent properties. Poly-3-hexylthiophene exhibits VIS reflection, similar to a metallic luster. In conjunction with a dielectric, ethylenedioxythiophenemethanol and ethylenedioxythiophene and their derivatives exhibit reversible electrochromic properties.

These properties can be modified and extended, for example, by mixtures with other polythiophene derivatives. In this case, for example, targeted IR, diffuse or shiny metallic VIS or UV properties can be set in defined band ranges. Furthermore, a corresponding modification contributes to increasing the long-term stability.

The liquid coatings show good solubility in solvents such as water, in alcohols and aromatics, for example in IPA, butanol, or ethanol. Therefore, when applying the coating, the viscosity of the coating composition can be defined by adjusting the solid content and the amount of solvent. As a result, it is possible to print both fine and coarse grid and / or line structures with the corresponding edge sharpness (line thickness tolerance as an example: ± 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 admixture with an initiator and / or catalyst.

The application of the electrically conductive monomers or polymers can be effected 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 roller application techniques.

As support substrates are for example carrier films, preferably flexible transparent plastic films, for example, from 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 to 700 .mu.m, preferably 5 to 200 .mu.m, particularly preferably 5 to 50 .mu.m.

Furthermore, metal foils, for example Al, Cu, Sn, Ni, Fe or stainless steel foils having a thickness of 5-200 μm, preferably 10 to 80 μm, particularly preferably 20-50 μm, may also serve as the carrier substrate. The films can also be surface-treated, coated or laminated, for example, with plastics or painted. Furthermore, paper or composites with paper, for example composites with plastics having a weight per unit area of 20 to 500 g / m ² , preferably 40 to 200 g / m ² , may also be used as the carrier substrates.

Furthermore, woven or nonwovens, such as continuous fiber webs, staple fiber webs and the like, which may optionally be needled mechanically or hydrodynamically and / or calendered, may be used as carrier substrates. Preferably such fabrics or webs of plastics, such as PP, PET, PA, PPS and the like, but it can also be woven or nonwovens made of natural, optionally treated fibers, such as viscose fibers are used. The nonwovens or fabrics used have a weight per unit area of about 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 mixture of monomer and initiator and / or catalyst and / or catalyst). FIG. 2 shows a further possibility for applying the monomer and the initiator and / or catalyst and / or catalyst, in FIG. 3 a possibility for applying two successive layers of the electrically conductive polymer, in FIG. 4 a diagram for the preparation of the Washing liquid and in Fig. 5 and Fig. 5a an inventive embodiment of the application device with reservoir and separate provided as Zudosiereinheiten storage containers.

In Fig. 1 to 3, 1 means the supporting substrate, 2 a storage vessel for mixing the monomer with the catalyst or the monomer, 2a the catalyst applying means (when only the monomer is provided in the storage vessel 2), 2b the storage vessel for the catalyst 3 a transfer roller, 4 a squeegee, 5 a dryer (IR, UV or convection dryer), 6 the wash 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 bar or dryer.

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

Form of salts), 9 a pressure control, 10 a pump, 11 den

Washing process, 12 filters, 13 - 17 ion exchangers, 18 the

Sanitation.

FIGS. 5 and 5 a show a preferred application device (2 or 2 b and 3 as shown in FIGS. 1 to 3) with associated additional immersion cylinder 3 a 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 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 means the outflow of the monomer / initiator and / or catalyst and / or catalyst mixture from the outer tub 22 in the reservoir. 3a means a dip 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 represents the reservoir for the monomer and 28 the reservoir for the initiator and / or catalyst and 29 the reservoir for the solvent.

It is preferably as shown in Fig. 5 from a reservoir 23 a, which is preferably double-walled and temperature-controlled to set a corresponding temperature, via a pump 23 b and a filter 23 c in the temperature-controlled inner tub 22 of the reservoir 2 (of Fig. 1) promoted. In the Innenwänne applied mixture through a distribution tunnel 25 and the distributor plate 26, which is provided with regularly arranged openings, evenly distributed. The Inπenwanne has on the inner surface of the shape of an approximately half-cylinder, said surface is dimensioned so that the plunger cylinder 3 a 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, the plunger cylinder 3a engages with approximately 1 / 3-1 / 2 of its circumference in the mixture conveyed into the inner tub. The temperature-controlled inner tub is dimensioned so that it on the side facing away from the drain 24 of the surrounding temperature-controlled outer tub side in about the dimension of a half-cylinder, but whose shape substantially continuing return plate up to a height of at least half of the diameter up to about 2 / 3 of the diameter of the submerged cylinder.

The dip cylinder now takes the polymer dispersion from the inner tub and transfers it to the transfer cylinder. In this case, the excess mixture, which is not absorbed by the transfer cylinder, now runs over the outside of the inner tub into the outer tub 21. Likewise, that portion which has not been applied to the application tool via the squeegee 4 (not shown in FIG. 5) returns to the outer sump.

Due to the orientation of the outer tub not plan in a plane, but with a slight slope from the side facing away from the drain side of the tub to the side on which the drain is located, the collected in the outer tub 21 mixture of the entire Lackauftragswerk is back in led the reservoir 23a. In the inner tub so there is always only from the reservoir at a defined temperature and with the inflow speed defined by the pump 23 b introduced mixture.

By avoiding the return of mixture not applied via the following cylinders and the doctor blade into the inner trough, the temperature mixture in the inner trough is kept correctly constant and also air intake is avoided. Furthermore, the temperature of the mixture in the Inner trough constantly via a temperature sensor (not shown in Figure 5) are controlled.

The drying of the applied layer then takes place through the drying devices 5 or the washing process in the washing station 6 for the removal of solvent residues (FIG.

However, the monomers or prepolymers are preferably applied to form the electrically conductive polymers and polymerized in situ (FIGS. 2, 3, and 5a).

In this case, both free-radical and redox or photo-initiator and / or catalysts, for example UV, can be used as the initiator and / or catalyst.

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

Optionally, in addition, a catalyst for accelerating the reaction may be added, for example, a Ziegler-Natta catalyst, or a Pt catalyst, in which case optionally, the added amount of initiator and / or catalyst may be lower.

In one embodiment, as shown in FIG. 2, the monomer can be provided in the storage vessel 2 and, if appropriate, applied to the carrier substrate analogously to the embodiment of the application device illustrated in FIG. The initiator and / or catalyst or optionally the additional catalyst is provided in storage vessel 2a and applied to the monomer present on the carrier substrate, wherein preferably an excess of initiator and / or catalyst is applied to achieve a complete polymerization of the polymer, such as in the following particularly preferred embodiment described in more detail. After the polymerization again the drying process, the washing process and optionally a further drying process (as described in more detail in the following particularly preferred embodiment of the method according to the invention)

In the particularly preferred embodiment, the corresponding monomer or prepolymer is preferably mixed with the initiator and / or catalyst (and optionally with an additional catalyst) and applied to the carrier substrate (analogous to FIG. 1, wherein in the storage vessel 2 the monomer / initiator and / or or catalyst mixture is provided).

The preferred embodiment of the application device has, as shown in Fig. 5a, in addition to the elements shown in Fig. 5 each have a reservoir for the monomer and a separate reservoir for the initiator and / or catalyst or the initiator and / or catalyst or additional catalyst mixture and for the optionally additionally metered in solvent. Preferably, the solvent is metered in via a viscosity regulator.

It is also possible to provide a solution of monomer or prepolymer and initiator and / or catalyst in a storage container and, in a second storage container, the solvent to be optionally metered in. The monomer / initiator and / or catalyst mixture is then in (strong) dilute solution in this case.

It is particularly preferred to use Fe (III) toluenesulfonate as the initiator / catalyst. Fe (III) toluenesulfonate is a radical initiator or catalyst which at the same time initiates a redox reaction during the polymerization. The Fe (III) ion acts as an initiator and the toluene solonate forms the matrix in the conductive polymer.

So is ethylenedioxythiophene-methanol as a monomer, for example, Baytron ^® OH Fa. Bayer, and Fe (III) toluenesulfonate, for example Baytron ^® C grades, for example, Baytron ^® CB-40 from Bayer, as initiator and / or Catalyst used, the polymer present on the carrier substrate after the polymerization is polyethylene dioxythiophene methanol / toluenesulfonate.

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 is about 1: 5 - 1: 100, preferably 1: 8 to 1: 80. The excess initiator and / or catalyst ensures complete and safe reaction of the entire monomer even during shorter available reaction times, thus ensuring that no deleterious residues remain. Furthermore, optimum film formation is achieved by this excess of initiator and / or catalyst.

The polymerization takes place depending on the solvent used! already at the time when a temperature is reached which causes evaporation of the solvent. In order to avoid premature or excessive polymerization prior to application to the carrier substrate in the storage vessels, or too rapid polymerization immediately after application to the carrier substrate, depending on the temperature prevailing in the storage vessels advantageously from the provided reservoirs monomer or solvent is metered in as needed via a pump, care should be taken during the addition of the solvent (for example, an alcohol such as propanol or n-butanol) that remain after the polymerization is not large amounts of solvent in the layer, which subsequently must be removed, so a balanced metering takes place. Preferably, however, the undesired polymerization is controlled by metering in the monomer, which is highly diluted in the solvent. By adjusting the solids content and the amount of solvent, and the temperature or by targeted prepolymerization in the paint pan, the viscosity is set manually or automatically defined.

By a known fall viscometer with automatic

Solvent adjustment, the viscosity can be adjusted and kept constant.

Alternatively, an early polymerization can also be prevented by the exact control of the temperature in the storage containers and in the commissioned unit, wherein the immersion cylinder or transfer and application cylinder should possibly be cooled or heated.

In a commissioned work designed in accordance with FIGS. 5 and 5a, therefore, the reaction kinetics are controlled by adjusting the proportions of the mixture components or the temperature, and at the same time a uniform homogeneous application of the polymer dispersion or of the monomer solution or of the monomer / initiator and / or catalyst mixture is achieved ,

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

Initiator and / or catalyst excess and optionally catalyst residues and other contaminating reaction products can also be removed in situ or optionally subsequently by treatment with a solvent, for example water, deionized water, deionized water, alcohols such as ethanol, propanols, butanols and the like or Water / solvent mixtures are removed from the layer.

Preferably, the initiator and / or catalyst excess is removed by water, which is treated, 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 adjustment of the ion content of the water, in particular the content of alkali and / or alkaline earth metal ions. Attachment of the ions present in the water to the O atoms of the ethylenedioxythiophene methanol units forms complexes, which alters the configuration of the macromolecules and thus shifts the band gap in the absorption spectrum and thus the absorption maximum. At the same time, the conductivity is variable by this complex formation and can therefore be defined by the content of ions in the water defined.

The water prepared as described above is therefore optionally adjusted to a defined ion content by addition of alkali and / or alkaline earth metal ions in the form of salts, for example sodium salts, for example NaCl or alkaline earth salts, such as Mg salts, for example MgCl ₂ .

The washing process is preferably carried out by applying the selected washing liquid by means of one or more nozzle bars, wherein preferably pressure and angle of the washing liquid impinging on the coating are adjustable.

The excess water on the polymer coating is squeezed off, wiped, dried, by suitable means such as squeezing devices, drying devices, air knife, or

Absauginheiten removed and fed into a recycling cycle.

The effluent from the process water is preferably circulated, where appropriate, if necessary, fresh water can be added. Wastewater saturated with initiator or initiator and catalyst is treated via a filter system and then via ion exchangers and / or by distillation. In order to ensure continuous operation, it is further possible for one group to be more than one, preferably one to five For example, at least one ion exchanger is in operation, another in stand-by mode and another in regeneration mode.

If necessary, finally, a washing process with pure, as described above recycled, fresh water can be connected.

If desired, highly volatile constituents can also be removed by drying with an IR dryer, a convection dryer and the like.

Depending on the use, the electrically conductive polymer layers may each have a thickness of 0.1-50 μm, preferably 0.5-10 μm. For certain uses thinner layers of 0.001 to 50 microns, preferably 0.05 to 10 microns are readily produced.

Furthermore, the layers according to the invention are excellently conductive. The extensibility of the layer can be variably controlled depending on the polymerization process and by adding a binder such as polyvinyl alcohols, optionally with melamine resins. The finer morphology of the poly-thiophene derivatives, for example, in particular also of the Pblyethylendioxythiophen-methanol compared to known thiophenes additionally ensures a constant conductivity under elongation.

The electrically conductive polymeric layers are generally resistant to temperature, it may possibly temperature resistances of> 100 ° C, in particular up to about 200 ⁰ C, can be achieved.

If desired, a transparency of> 80% can be achieved with the electrically conductive polymer layers according to the invention, or in Depending on the polymer produced or the mixture produced a targeted reflection can be adjusted.

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

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

The adhesion of the polymer coating to the carrier substrate is generally very good, particularly good adhesion is achieved with the use of Polyethylendioxythiophen - methanol by the higher polarity. The electrically conductive polymers can be present both on the entire surface as well as partially on the carrier material.

The application of the electrically conductive polymers according to one of the embodiments of the method described in the form of characters and patterns, flat or linear, wavy or zigzag and similar or analogous structures, such as guilloches, along and / or transversely to the machine direction of the substrate. Furthermore, the conductive polymers can also form recesses in the form of characters, patterns, flat, line, wave, zigzag structures and / or guilloches on the substrate.

Line-shaped or analogous structures have a conductivity directed in a preferred direction according to the orientation of the structures. In addition, these structures provide additional security against destruction by transverse cracks in this and possibly above and / or underlying layer, since they are prevented from tearing at the interstices. If such an electrically conductive layer by an additional layer, such as a lacquer layer or by laminating protected, the gaps or recesses ensure improved sealing of the conductive polymer layer.

If appropriate, these structures also represent a 2-dimensional coding.

Although the electrically conductive polymeric layers are very stable mechanically and thermally, but may be sensitive to moisture, these layers are preferably not directly on the surface of the substrate.

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

The widths of the lines, waves or zigzag structures or guilloches can be, for example, 0.05-10 mm, preferably 0.1-0.3 mm, those of the cross-connections 0.5-100 mm, preferably 1-10 mm.

For partial application, a solvent-soluble paint or a soluble paint can be applied to the carrier substrate or any layers already thereon. Subsequently, the conductive polymer is applied to this layer, whereupon the soluble color in the uncoated areas is removed by means of the appropriate solvent, optionally with mechanical assistance. However, it is also possible first to apply a suitable adhesion promoter partially in the desired form to the carrier substrate, then to apply the electrically conductive polymer over the entire area, whereupon the polymer is applied in those areas where no adhesion promoter is present by appropriate measures based on the basic adhesion are matched to the electrically conductive polymer, can be replaced again.

Furthermore, the partial application can also take place according to the method described in DE 100 25 522 A1.

The electrically conductive polymer layer can also be adjusted to be adhesive or releasable.

In order to increase the conductivity, it is also possible for the time being to apply a layer of the electrically conductive polymer and then to apply a further layer of the electrically conductive polymer, for example by in situ polymerization. Furthermore, the electrically conductive polymer layers according to the invention can also be applied particularly advantageously in conjunction with an inorganic, preferably metallic or pigmented conductive layer. Not only is there an improvement in the electrical conductivity of the coated substrate but also an additional assurance of proper function and identifiability.

Due to the better extensibility of the electrically conductive polymers, malfunctions that can occur as a result of fine and very fine cracks in the inorganic conductive layer can be bridged by the electrically conductive polymer layer.

A multilayer structure of a full-area or partial layer of a conductive polymer with printed over it linear, wavy and the like structures of the same polymer leads to different Conductivities in the different directions, for example parallel or transversely to the machine direction, but also at any angle to the machine direction.

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

Optionally, the polymeric conductive primer layer and the second polymeric conductive layer deposited thereover may also be separated by an insulator layer.

But there are also constructions of more than 2 each full-area and / or partial polymeric electrically conductive layers, which may possibly be separated by insulator layer (s) conceivable.

Preferably, the electrically conductive layer (s) of polymer (s) are not in direct contact with metallic layers and are separated therefrom by an insulator layer.

Furthermore, the electrically conductive polymer layers, as well as, if appropriate, the additional inorganic metallic and / or pigmented electrically conductive layers, can be coded as patches and thus also be applied in a machine-readable and / or structured manner. Furthermore, the electrically conductive polymer layers can subsequently be embossed inline or offline, perforated or microperforated.

The carrier substrate may already have functional or decorative layers, or further layers may be applied after the conductive layer has been applied. The carrier substrates may additionally have a lacquer layer, which may be unstructured or structured, for example embossed. The lacquer layer can be, for example, a release-capable transfer lacquer layer, it can be crosslinked or crosslinkable by radiation, for example UV radiation, and can be scratch-proof and / or antistatic. Both aqueous and solid coating systems, in particular lacquer systems based on polyester acrylate or epoxy acrylate, are rosin, acrylate, alkyd, melamine, PVA, PVC, isocyanate, urethane systems which are conventionally and / or reactively curing and / or can be radiation-curing.

As color or lacquer layers, a wide variety of compositions can be used in each case. The composition of the individual layers may in particular vary according to their purpose, that is to say whether the individual layers serve exclusively for decoration purposes or should be a functional layer or whether the layer should be both a decoration ais and a functional layer.

These layers may be pigmented or unpigmented. As pigments, it is possible to use all known pigments, such as, for example, titanium dioxide, zinc sulfide, kaolin, ITO, ATO, FTO, aluminum, chromium oxides and silicon oxides, and also colored pigments. In this case, solvent-based coating systems and systems without solvents can be used.

Suitable binders are various natural or synthetic binders.

For example, the functional layers may have certain magnetic, chemical, physical and also optical properties.

To adjust the magnetic properties, paramagnetic, diamagnetic and also ferromagnetic materials, such as iron, nickel and Cobalt or its compounds or salts (for example, oxides or sulfides) can be used.

Particularly suitable for use in conjunction with the electrically conductive polymer layers according to the invention are magnetic pigment paints with pigments based on Fe oxides, iron, nickel cobalt and their alloys, barium or cobalt ferrite, hard and soft magnetic iron and steel grades in aqueous or solvent-containing dispersions. The solvents used are, for example, i-propanol, ethyl acetate, methyl ethyl ketone, methoxypropano! and their mixtures in question.

The pigments are preferably incorporated in acrylate polymer dispersions having a molecular weight of from 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 visualized by visible dyes or pigments, luminescent dyes or pigments which fluoresce or phosphoresce in the visible, in the UV region or in the IR region, effect pigments, such as liquid crystals, pearlescent, bronzes and / or multilayers - 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.

Various properties can also be combined by adding various additives mentioned above. Thus, it is possible to use colored and / or conductive magnetic pigments. All mentioned conductive additives can be used.

Especially for the dyeing of magnetic pigments it is possible to use all known soluble and non-soluble dyes or pigments. So can For example, a brown magnetic paint by addition of metals in their color metallic, for example silvery be set.

For printing soluble layers and also for applying partial conductive layers according to the invention, the ink or lacquer used can be soluble in a solvent, preferably in water, but it can also be a dye soluble in any solvent, for example in alcohol, esters and the like become. The color or the colored lacquer can be customary compositions based on natural or artificial macromolecules. The color may be pigmented or unpigmented. As pigments, all known pigments can be used. Particularly suitable are TiO ₂ , ZnS, kaolin and the like.

If a soluble color layer is used, it may optionally be removed after application of another layer in the process according to the invention by a suitable solvent adapted to the composition of the color layer in order to be able to produce codings in the form of characters and / or patterns of any possible type. Subsequently, the color layer is removed by a suitable solvent, which is adapted to the composition of the color layer. The application of paint is preferably water-soluble. Optionally, the separation can be supported by mechanical action.

Furthermore, for example, insulator layers can be applied. As insulators, for example, organic substances and their derivatives and compounds, for example, color and lacquer systems, e.g. Epoxy, polyester, rosin, acrylate, alkyd, melamine, PVA, PVC, isocyanate, urethane systems which may be radiation-curable, for example by heat or UV radiation.

Such layers can be particularly in the production of multilayer structures, for example, for printed circuit boards between 2 or more electrically conductive polymer layers and / or electrically conductive metallic and / or pigmented layers which must be separated from each other.

These layers may be applied by known methods such as sputtering, 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 about 0.001 to 50 microns, preferably 0.1 to 20 microns.

Furthermore, partial or full-surface metallic layers may 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. As the metal layer, layers of Al, Cu, Fe, Ag, Au, Cr, Ni, Zn and the like are suitable. 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 applied over the whole area as well as partially, with registration and register accuracy, optionally also at least partially overlapping with the already existing layers in a known manner, for example in a metalization or demetallization process, by printing and the like.

The product is therefore optionally suitable for packaging as a security element in data carriers, in particular documents of value such as identity cards, cards, banknotes or labels, seals and the like, but also as packaging material, for example in the pharmaceutical and food industries, for example in form Blister foils, cartons, covers, foil packaging and the like. Such products 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 devices, electrode assemblies, as heatable films, for example for windshields, as a transparent reflection layer under holograms and / or structured layers and the like. Furthermore, because of their excellent optical properties, they can be used as a "high refractive index" layer, as decorative or optical elements, for example in architecture, etc. For use as security features, the substrates or foil materials are preferably cut into strips and threads. wherein the width of the strips or threads may preferably be 0.05 - 10 mm.

Examples:

Example 1 :

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

Adhesion promoter (A 1120, OSI) is applied from a storage vessel via a transfer roller, a mixture of ethylenedioxythiophenmethanol and iron (III) toluenesulfonate and polyvinyl alcohol in the ratio 1:10:10 applied 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%.

The layer is 100% resistant to tesa and 40% stretchable and thus deep drawable with low conductivity loss.

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

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

Property.

Example 2:

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

Iron (III) toluenesulfonate in a ratio of 1:10 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 purple color.

When heated to about 100 ⁰ C, the layer shows a color change from non-fluorescent violet 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 of a magnetic ink on the basis of Fβ ₃ θ ₄ in an acrylate polymer dispersion and a 0.2 micron layer of a fluorescent ink laminated by means of a commercially available laminating adhesive.

Subsequently, the surfaces were provided with a heat sealing lacquer.

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

Example 4:

FIG. 6 shows a substrate according to the invention with several additional functional features.

1 is a transparent flexible carrier substrate, 2 is a coating with fluorescent properties, 4 is a primer layer, 5 is the patterned polymeric conductive layer and 6 is a protective or adhesive layer, for example a heat-sealable adhesive layer, 7 a laminating adhesive layer and 8 an opaque layer with recesses.

Claims

claims:

1) substrates having at least one electrically conductive layer, characterized in that the electrically conductive (s) layer (s) of thiophene derivatives or a mixture of thiophene derivatives (s), the at least one additional to the conductivity, physical, mechanical has readable property and is printable with high edge sharpness regardless of line width.

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) ethylenedioxythiophene- 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-; or mixtures of these polymers or mixtures of these polymers with other polythiophene derivatives is (s).

3) Substrates according to claim 1 or 2, characterized in that the layer (s) of electrically conductive polymers are present partially or completely 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, planar, line, wave, zigzag structures and / or guilloches is present on the substrate /are.

5) Substrates according to one of claims 1 to 4, characterized in that the electrically conductive polymers form recesses in the form of characters, patterns, flat, line, wave, zigzag 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 line, wave, zigzag-shaped structures and / or guilloches has a direction of preferred conductivity / have.

7) Substrates according to claim 6, characterized in that the structures are longitudinal or transverse 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 property.

11) Substrates according to claim 10, characterized in that the electrically conductive polymer layer is IR-reflective.

12) Substrates according to claim 10, characterized in that the electrically conductive polymer layer has thermochromic properties.

13) Substrates according to claim 10, characterized in that the electrically conductive polymer layer has 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 conductive (s) polymer layer (s) has a defined adjustable conductivity / have.

16) Substrates according to one of claims 1 to 15, characterized in that the electrically conductive (s) polymer layer (s) in correlation to the adjustable conductivity have a defined color.

17) Substrates according to one of claims 1 to 16, characterized in that in addition further color, lacquer, metallic layers and / or surface structures are present, wherein metallic and conductive layers directly or not directly adjoin one another.

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 (s) layer (s) encoded as patches, machine-readable and / or structured are applied.

20) Substrates according to one of claims 1 to 19, characterized in that the electrically conductive polymer layers are then embossed inline or offline, perforated, microperforated.

21) film material having at least one electrically conductive layer, characterized in that the electrically conductive layer (s) of thiophene derivatives or a mixture of thiophene derivatives (s), the has at least one physical, machine readable property which is additional to the conductivity and which can be printed with high edge definition irrespective of the line width.

22) film 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) ethylenedioxythiophene- 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-; or mixtures of these polymers or mixtures of these polymers with other polythiophene derivatives is (s).

23) film material according to claim 22, characterized in that the layer (s) of electrically conductive polymers are present partially or completely on the substrate.

24) film material according to one of claims 21 to 23, characterized in that the layer (s) of electrically conductive polymers in the form of characters, patterns, planar, line, wave, zigzag structures and / or guilloches is present on the substrate /are.

25) film material according to one of claims 21 to 23, characterized in that the layer (s) of electrically conductive polymers form recesses in the form of characters, patterns, flat, line, wave, zigzag-shaped structures and / or guilloches on the substrate ,

26) film material according to one of claims 21 to 25, characterized in that the layer (s) of electrically conductive polymers in the form of line, wave, zigzag structures and / or Guillochen has / have a directionally preferred conductivity.

27) film material according to claim 26, characterized in that the structures are longitudinal or transverse or at any angle to the machine direction.

28) film material according to one of claims 21 to 27, characterized in that the structures represent a 2-dimensional coding.

29) Film material according to one of claims 21 to 28, characterized in that the conductive layers do not lie on the surface of the substrates.

30) Film material according to one of claims 21 to 29, characterized in that the electrically conductive polymer layers have a further machine-readable property.

31) film material according to claim 30, characterized in that the electrically conductive polymer layer is IR-reflective.

32) film material according to claim 30, characterized in that the electrically conductive polymer layer has thermochromic properties.

33) Film material according to claim 30, characterized in that the electrically conductive polymer layer has electrochromic properties. 34) Film material 'according to claim 30, characterized in that the electrically conductive polymer layer has a diffuse or metallically glossy VIS reflection.

35) film material according to one of claims 21 to 34, characterized in that the conductive (n) polymer layer (s) has a defined adjustable conductivity / have.

36) film material according to one of claims 21 to 35, characterized in that the electrically conductive (s) polymer layer (s) in correlation to the adjustable conductivity have a defined color.

37) film material according to one of claims 21 to 36, characterized in that in addition further color, lacquer, metallic layers and / or surface structures are present, wherein metallic and conductive layers do not directly adjoin one another.

38) Film material according to one of claims 21 to 37, characterized in that additional inorganic metallic and / or pigmented electrically conductive layers are applied.

39) film material according to one of claims 22 to 38, characterized in that the electrically conductive (s) layer (s) encoded as patches, machine-readable and / or structured applied (are).

40) Film material according to one of claims 20 to 39, characterized in that the electrically conductive polymer layers are subsequently embossed inline or offline.

41) 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, documents of value, data carriers, banknotes, packaging, and the like, characterized in that they have been produced, if appropriate, by packaging from one of the substrates according to claims 1-20 or the film material according to claims 21-41.

42) security papers, value documents, data carriers, banknotes, packaging materials, packaging, characterized in that they have at least one security element according to claim 41.

43) Process for the preparation of substrates with electrically conductive layers, characterized in that the monomers or prepolymer are applied to the carrier substrate and polymerized in situ.

44) Process according to claim 43, characterized in that in the in situ polymerization catalyst residues are removed in situ.

45) Method according to one of claims 43 or 44, characterized in that monomer to initiator and / or catalyst in a weight ratio of 1: 5 to 1: 100 are submitted or applied.

46) Process according to one of claims 43 to 45, characterized in that are used as the monomer Baytron ^® types and as an initiator and / or catalyst Baytron ^® C types.

47) Method according to one of claims 41-46, characterized in that an additional catalyst is used.

48) Method according to one of claims 41 - 47, characterized in that the application of the monomer and the initiator and / or Catalyst or the monomer / initiator and / or catalyst mixture temperature controlled takes place.

49) Process according to any one of claims 41 - 48, characterized in that initiator and / or catalyst residues and / or other undesirable reaction products are removed by washing with a suitable solvent.

50) Process according to claim 49, characterized in that initiator and / or catalyst residues and / or other undesirable reaction products by washing with by reverse osmosis, ion exchanger, distillation and / or physical Aufbreitungsanlagen treated water with a defined content of alkali and / or alkaline earth Ions are removed.

51) Method according to one of claims 41- 50, characterized in that the water used for washing is recycled and is processed by filtration, ion exchanger and / or distillation.

52) A method according to any one of claims 41 to 51, characterized in that as needed by reverse osmosis, ion exchanger, distillation and / or physical Aufbreitungsanlagen treated fresh water is supplied to the wash water circuit.

53) A method according to any one of claims 41 to 52, characterized in that a final washing step is carried out with treated by reverse osmosis, ion exchanger, distillation and / or physical Aufbreitungsanlagen fresh water.

54) Method according to one of claims 41 - 53, characterized in that the washing process is carried out inline or out of line. 55) Method according to one of claims 41 to 54, characterized in that on the carrier substrate already functional and / or decorative layers are present and / or subsequently applied.

56) Use of the substrates according to one of claims 1 - 20 and / or Foüenmaterialien according to any one of claims 21 - 41 optionally after packaging as a security element in data carriers, in particular documents of value such as identity cards, cards, banknotes or labels, seals, as packaging material in the pharmaceutical and Food industry, 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 assemblies, as heatable films, such as windshields, as transparent reflection layers under holograms and / or structured layers, and as a high refractive index layer.