EP2770104B1 - Electrically conductive paper structure - Google Patents

Electrically conductive paper structure Download PDF

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Publication number
EP2770104B1
EP2770104B1 EP14156382.5A EP14156382A EP2770104B1 EP 2770104 B1 EP2770104 B1 EP 2770104B1 EP 14156382 A EP14156382 A EP 14156382A EP 2770104 B1 EP2770104 B1 EP 2770104B1
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EP
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Prior art keywords
range
carbon fibers
paper fabric
particularly preferably
paper
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EP14156382.5A
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German (de)
French (fr)
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EP2770104A1 (en
Inventor
Peter Helfer
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Helfer Peter
Reso Oberflaechentechnik GmbH
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Reso Oberflachentechnik GmbH
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/46—Non-siliceous fibres, e.g. from metal oxides
    • D21H13/50—Carbon fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
    • D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration

Definitions

  • the present invention relates to an electrically conductive paper structure and a method for its production, as well as the use of the electrically conductive paper structure, for example as a heating element.
  • Carbon fiber reinforced plastics are also increasingly being used as lightweight construction material in industry.
  • CFRP carbon fiber reinforced plastics
  • paper which is made, inter alia, of vegetable cellulose fibers, be it pulp, mechanical pulp or the like, has substantially electrical insulating properties, to some extent also from the moisture content of the paper when used to be influenced. So it is known, for example, paper as insulating material for
  • the resistivity of paper at standard conditions is greater than 10 ' ⁇ m and the electrical conductivity is less than 10 -10 S / m, so conventional paper is referred to as a nonconductor.
  • the inventively electrically conductive paper structure has as essential material components a mixture of fibrous materials, chemical additives and residual moisture.
  • the mixture of fibers comprises at least cellulosic Fasersoffe and carbon fibers, in particular recycled carbon fibers whose mixing ratio is selected so that the specific resistance of the finished paper structure under standard conditions in a range between 10 -1 ⁇ m and 10 -6 ⁇ m.
  • the prior art such as in the US 3367851 by Manuel Filreis , however, only electrically conductive paper structure is known with a resistivity between 0.36 • 10 -3 ⁇ m and 0.6 ⁇ m.
  • cellulosic fibrous materials are understood as meaning all fibrous materials, in particular of natural origin, which are preferably selected from a group of fibrous materials, which are wood fibers, hemicellulars, thermomechanical pulp, rags or cotton fibers, chemically digested cellulose such as sulfate or sulfite pulp, mechanical pulp , chemically modified wood pulp, recycled pulps, combinations thereof, and the like.
  • carbon fibers are preferably understood as meaning industrially produced fibers which are formed from carbonaceous material and are converted, for example, by pyrolysis, into a graphitic carbon arrangement.
  • Such fibers can be produced isotropically or anisotropically and usually have a diameter of about 5 microns to 8 microns.
  • These single fibers are bundled during processing into bundles (rovings) with 1,000 to 400,000 individual fibers and can then be further processed.
  • Carbon fibers are highly conductive both electrically and thermally.
  • carbon fibers are understood to be fibers from a group which are high-strength carbon fibers, in particular high-tensity / high tenacity, intermediate modulus, high modulus, especially high modulus, ultra modulus, ultra high modulus, ultra modulus strength, high stiffness / high strength carbon fibers, combinations thereof and the like having.
  • CFRP Carbon fiber reinforced plastics
  • thermochemical cleavage pyrolysis
  • epoxy resin is removed from the carbon-containing plastic (in particular by sublimation).
  • the fibrous materials thus obtained have a preferred length distribution or a corresponding center of gravity, preferably in a range between 1 ⁇ m to 50,000 ⁇ m, preferably in a range between 8,000 ⁇ m to 50,000 ⁇ m, more preferably in a range between 1 ⁇ m to 8,000 ⁇ m and more preferably in a range between 5,000 ⁇ m to 8,000 ⁇ m.
  • This length distribution is in both the use of primary carbon fibers, as well as recycled Carbon fibers of advantage, since so can mix the corresponding carbon fibers well and in particular homogeneously with the other cellulose-containing fibers of the stable mixture for the production of the paper structure.
  • the aim in particular is to ensure the most homogeneous possible distribution of the at least two pulp constituents both in the suspension for producing a paper structure and in the paper structure itself.
  • the proportion of carbon fibers in the paper structure is greater than 35% or between greater than 35% and 99%, preferably between 45% and 85%, more preferably between 50% and 80%, most preferably over 50%. It should also be considered according to the invention that with the increase in the proportion of primary and / or recycled carbon fibers, the specific resistance of the paper structure thus formed decreases and the conductivity of the paper thus formed increases.
  • the advantage of an increased proportion of carbon fibers in the paper structure are, inter alia, improved conductivity, the reduction of the electrical resistance in the sheet or paper structure and the associated higher line pickup.
  • the increased use of carbon fibers can be achieved by the selected fiber length distribution of the carbon fibers and / or the combination with the paper pulp. This can be, for example, cotton fiber (rags), which is specifically fibrillated in particular by targeted grinding (Holéesmahlung) and thus can provide a particularly high strength potential for the paper structure to be produced.
  • the specific resistance of the paper structure according to the invention is in the range of 10 -2 ⁇ m and 10 -5 ⁇ m, preferably between 10 -2 and 10 -4 ⁇ m, more preferably between 10 -2 to 10 -3 ⁇ m, most preferably at about 30 -2 ⁇ m and 50 -2 ⁇ m, respectively.
  • the chemical additive (s) will be selected from a group which in particular comprises retention aids, drainage aids, retention agent dual systems or microparticle systems,
  • wet and dry residues, sizing agents, fillers and / or pigments in particular selected from a group of talc, titanium dioxide, aluminum hydroxide, bentonite, barium sulfate, calcium carbonate, kaolin, defoamers, deaerators, biocides, enzymes, bleaching aids, optical brighteners, dyes, shading dyes, Contaminant catcher, precipitating agent (fixer), wetting agent, pH regulators.
  • the chemical additive can also be selected from a group of preferably water-soluble polymers which in particular amine-containing polymers, polyethyleneimine, pyrolidine, polyamides, polyacrylamide, aridine, proteins, peptides, polyether-containing polymers, in particular polyethylene oxide, polyether, hydroxyl-containing polymers, in particular Starch, carboxymethylcellulose, polyvinyl alcohol, charged polymers, in particular cationic polymers, in particular cationic starch, corn starch, potato starch, wheat starch, rice starch, polymers containing ammonium groups, anionic polymers, in particular anionically modified polyacrylamides, sulphonated polymers, inorganic salts with high charge density, in particular aluminum salts, aluminum ( III) chlorides, aluminum sulfate, sodium aluminate, inorganic charged particles / pigments, in particular bentonite, montmorillonite, sodium silicate, wet strength agent, especially epichlorohydrin resins, gly
  • the paper structure according to the invention has a basis weight according to DIN EN ISO 536 which is in the range from 15 g / m 2 to 1,000 g / m 2 , preferably from 20 g / m 2 to 800 g / m 2 , more preferably between 20 g / m 2 to 300 g / m 2 , very particularly preferably above 40 g / m 2 .
  • Such a paper structure furthermore has a power consumption, at least as a function of the amount of carbon fiber used, which is in the range from 50 W / m 2 to 5,000 W / m 2 , preferably in the range from 100 W / m 2 to 3,700 W / m 2 preferably in the range from 100 W / m 2 to 1000 W / m 2 , very particularly preferably in the range from 250 W / m 2 to 750 W / m 2 .
  • a temperature in the range of 15 ° C to 130 ° C preferably a surface temperature in the range of 35 ° C to 100 ° C, more preferably a surface temperature in the range of 15 ° C to 99 ° C, most preferably a surface temperature in the range of 75 ° C to 130 ° C to achieve.
  • the present invention is also achieved by a method for producing the corresponding paper structure and its use for producing specific products.
  • At least a portion of the carbon fibers are recycled carbon fibers using, for example, pyrolytic treatment of the carbon fiber composites with resin removal by sublimation.
  • Such recycled carbon fibers may be carbon fiber sections or even carbon fiber composites such as roving residues.
  • the invention further includes the use of the electrically conductive paper structure as a heating paper, in particular as a heating element in floors, walls, wallpaper, containers, fabrics, clothing, table tops, hot plates, heating mats, car interior heaters, especially door, seat, dashboard heaters, the Radiation protection, combinations thereof and the like.
  • the electrically conductive paper structure according to the invention is also suitable, in addition to electrically conductive function also to be used in particular for the shielding of radiation, such as electromagnetic radiation.
  • electrically conductive paper structures can thus be used in technical installations, in electronic assemblies, in living spaces and in many other applications in order to effectively suppress electromagnetic radiation and thus have a shielding effect. It can also be used to protect people and animals against electrical, magnetic and electromagnetic fields.
  • electrically conductive paper structures can strongly influence the radiation extinction coefficient or change it in favor of the environment.
  • Another advantage of the electrically conductive paper structure according to the invention is that the workup of a carbon fiber composite material, in particular CFK is pyrolytic, wherein the resin is removed by sublimation at a temperature of 550 ° C - and thus the carbon fiber is exposed without damage. As a rule, uneven fiber lengths are present. By means of a downstream comminution stage, these fibers are homogenized and brought to a defined length range.
  • the carbon fibers which are pyrolyzed and prepared in various shapes and sizes, are mixed in the stock preparation with the waste paper suspension and then fed together to the two-dimensional papermaking process.
  • a further advantage of the paper structure according to the invention is that the paper structure can be produced relatively inexpensively, the use of recycled fibers both with respect to the carbon fibers and the cellulose fibers allows the paper structure provides a high flexibility / malleability (mobility), the paper texture with lower area related mass is easy to handle, easy to use and easy to store, and also easy and specific to equip.
  • the processing of the recycled carbon fiber takes place to the inventive electrically conductive paper structure with a proportion of 1 to 99% of the corresponding recycled carbon fiber from a pulp suspension in the papermaking process to a paper sheet.
  • the basis weight may be between 20 g / m 2 and 1,000 g / m 2 .
  • the carbon fiber-containing paper structure can be electrified according to the invention.
  • the electrification is carried out, for example, with a low current between 12 V and 40 V, preferably with 12 V or 24 V (DC, AC), whereby the carbon fiber-containing paper structure can be used as a heating surface.
  • a possible advantage of such a paper structure is, inter alia, that the material retains the paper character, remains supple and how classic paper can be shaped and trimmed in all forms. Laminating on stone, textiles or other materials is also possible.
  • a corresponding paper structure can be used as a wall heating and contribute by the arrangement on cold walls such as basements to avoid cold spots. It is not necessary to provide particularly high surface temperatures, but it is sufficient the paper texture to room temperature to warm up. Thus, the formation of moist spots and thus the risk of mold growth can be significantly reduced.
  • the measurement of the resistance values took place with an LCR measuring device of the manufacturer Hewlett Packard.
  • the measuring voltage for determining resistance was 3 V.
  • the measuring cell had a circular center contact and an annular external contact at a uniform distance of 1 cm from the center.
  • FIGS. 1 to 3 are shown a top plan photograph of the inventive electrically conductive paper structure with recycled carbon fibers.
  • the arrangement of the rod-shaped, dark to black-colored recycled carbon fibers in the paper structure are clearly recognizable in contrast to the wastepaper-containing paper pulp used here.
  • FIG. 4 Graphical is the development of the paper strength of the paper structure as a function of the carbon fiber content in the paper structure.
  • the abscissa represents the proportion of recycled carbon fibers in the paper structure in steps of 0, 20, 50 and 80% and the ordinate indicates the strength starting from 100% without a carbon fiber fraction. It can be seen clearly how the strength decreases with an increase in carbon fibers and, with an 80% share of carbon fibers, only about 30% of the initial value.
  • FIG. 7 is the graphical representation of the power consumption of a paper structure per square meter (P spec in W / m 2 ) as a function of the surface temperature in ° C.
  • P spec in W / m 2 the power consumption of a paper structure per square meter
  • FIGS. 8 and 9 show the development of the electrical resistance in ohms as a function of the surface temperature in ° C.
  • the resistance of the paper structure decreases by approx. 20%.
  • the paper structure of the invention was found that, for example, microwave radiation (frequency about 2450 MHz) could be reduced by a corresponding paper texture by more than 95%.
  • the power of the source was about 8 mW / cm 2 and behind the paper structure at 0.4 mW / cm 2 .
  • a fleece made of carbon fibers was processed.
  • the material was folded on the side edges and silver-colored wires were glued into the folds with a black (sooty) adhesive.
  • the second fleece was also made of carbon fiber.
  • the material was also folded at the side edges and copper wires were glued into the folds with a black (sooty) glue.
  • the fabric consisted of a mixture of carbon fibers and non-electrically conductive fibers.
  • the material was refolded at the side edges and copper wires were glued into the folds with a black (sooty) glue.
  • the fabric of the first experiment was difficult to glue. As a result of the bonding and the embedded wires, the fabric warped and did not adhere properly to the plasterboard - waves formed, which needed to be pressed more often, until the adhesive finally set sufficiently to adhere the fabric to the panel on its own accord , The folding / gluing formed irregular edges on the plate. Upon further processing, the fabric was weak from cohesion. Malerkrepp could not be detached without destroying it. Otherwise, the further construction (priming / coating) was unproblematic. The folding / gluing causes a very different layer thickness in the area of the tissue. However, the adhesive used does not cause any problems with respect to the suction power of the substrate.
  • the fabric from the second experiment could be stuck even with difficulty.
  • the fabric warped and did not adhere properly to the plasterboard - waves formed, which had to be pressed more often, until the adhesive had finally set so far to adhere the tissue to the plate by itself.
  • the folding / gluing formed irregular edges on the plate.
  • the tissue of the second experiment is cohesively weak, but it is stronger than the tissue of the first experiment.
  • the painter's crepe peeled off better than in experiment 1. Otherwise, the further structure (priming / coating) was unproblematic.
  • the folding / gluing causes a very different layer thickness in the area of the tissue. This approach is clearly visible.
  • the adhesive used does not cause any problems with respect to the suction power of the substrate. During operation, the lateral tracks heated disproportionately and very quickly.
  • the fleece was energized with a voltage of 20-30 V.
  • the fabric of Trial Three was easily processed, reacted well to the adhesive, and adhered well to the GKP. By folding / gluing slightly irregular edges formed on the plate. The further processing was unproblematic. In contrast to the tissue from trials one and two, the painter's crepe was best removed. The folding / gluing causes a different layer thickness in the area of the tissue. However, the adhesive used does not cause any problems with respect to the suction power of the substrate. During operation, the lateral tracks heated disproportionately and very quickly.
  • the paper structure / fleece was supplied with a voltage of 20-30 V.

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Description

Die vorliegende Erfindung betrifft ein elektrisch leitendes Papiergefüge und ein Verfahren zu dessen Herstellung, sowie die Verwendung des elektrisch leitenden Papiergefüges zum Beispiel als Heizelement.The present invention relates to an electrically conductive paper structure and a method for its production, as well as the use of the electrically conductive paper structure, for example as a heating element.

Aus dem Stand der Technik sind flächige Gebilde bekannt, welche zum Beispiel aus Kohlenstoffnanoröhrchen hergestellt werden. Es handelt sich hierbei u.a. um sogenanntes Bucky-Papier, welches durch die Filtration aus einer Suspension von Kohlenstoffnanoröhrchen hergestellt wird. Nachteilig hierbei ist jedoch, dass die Herstellung solcher flächigen Gebilde sehr aufwendig und damit teuer ist. Darüber hinaus werden zur Herstellung dieser Systeme ausschließlich Kohlenstoffnanoröhrchen verwendet. Neben diesen sehr speziellen Verwendungsmöglichkeiten von Kohlenstoff werden in der Industrie auch zunehmend kohlenstofffaserverstärkte Kunststoffe (CFK) als Leichtbaumaterial verwendet. Hierbei setzt sich der kohlenstofffaserverstärkte Kunststoff aus einzelnen Kohlefasern, Kohlenstofffaserrovings oder Kohlefasergewebe zusammen, welche mit Epoxidharz zu einer Matrix verbunden werden. Beispielhaft für so eine Anwendung ist die US6540874 von Ling-Chen , in dem die Carbonfasern erst in die gewünschte Länge geschnitten werden, dann mit Wasser und Harz zusammengemischt und gemahlen wird. Nachteilig ist hierbei jedoch, dass der entsprechende kohlenstofffaserverstärkte Kunststoff in seiner Herstellung relativ teuer ist, jedoch im Vergleich zu anderen Materialien nur relativ schwer wiederaufbereitet und zu neuen Produkten verarbeitet werden kann.Surface structures are known from the prior art, which are produced, for example, from carbon nanotubes. These include so-called Bucky paper, which is produced by filtration from a suspension of carbon nanotubes. The disadvantage here, however, is that the production of such flat structures is very complicated and therefore expensive. In addition, only carbon nanotubes are used to make these systems. In addition to these very special uses of carbon, carbon fiber reinforced plastics (CFRP) are also increasingly being used as lightweight construction material in industry. Here, the carbon fiber reinforced plastic from individual carbon fibers, carbon fiber rovings or carbon fiber fabric together, which are connected with epoxy resin to form a matrix. Exemplary of such an application is the US6540874 to Ling-Chen in which the carbon fibers are first cut to the desired length, then mixed together with water and resin and ground. The disadvantage here, however, that the corresponding carbon fiber reinforced plastic in its production is relatively expensive, but compared to other materials only relatively difficult to recycle and can be processed into new products.

Im Stand der Technik ist es des weiteren bekannt, dass Papier, welches u.a. aus pflanzlichen Cellulosefasern - sei es Zellstoff, Holzstoff oder dergleichen - hergestellt wird, im wesentlichen elektrisch isolierende Eigenschaften hat, die in einem gewissen Umfang auch vom Feuchtigkeitsgehalt des Papiers bei seinem Einsatz beeinflusst werden. So ist es zum Beispiel bekannt Papier als Isoliermaterial zurIt is further known in the prior art that paper, which is made, inter alia, of vegetable cellulose fibers, be it pulp, mechanical pulp or the like, has substantially electrical insulating properties, to some extent also from the moisture content of the paper when used to be influenced. So it is known, for example, paper as insulating material for

Herstellung von Kondensatoren zu verwenden. Üblicherweise ist der spezifische Widerstand von Papier bei Standardbedingungen größer als 10'° Ωm und die elektrische Leitfähigkeit kleiner als 10-10 S/m, so dass man konventionelles Papier als Nichtleiter bezeichnet.Production of capacitors to use. Typically, the resistivity of paper at standard conditions is greater than 10 'Ωm and the electrical conductivity is less than 10 -10 S / m, so conventional paper is referred to as a nonconductor.

Ausgehend von diesem Stand der Technik ist es Aufgabe der vorliegenden Erfindung ein Papier bereit zu stellen, bei welchem die elektrischen Leiteigenschaften gezielt beeinflusst werden können, um insbesondere den Einsatzbereich von Papier bzw. Papiergefüge zu erweitern bzw. zu verbessern.Based on this prior art, it is an object of the present invention to provide a paper in which the electrical conduction properties can be influenced in a targeted manner, in particular to expand or improve the field of application of paper or paper structure.

Die vorstehende Aufgabe wird durch elektrisch leitendes Papiergefüge gemäß Anspruch 1 und das Verfahren zu dessen Herstellung gemäß Anspruch 15 gelöst. Bevorzugte Ausführungsformen des erfindungsgemäßen elektrisch leitenden Papiergefüges und dessen Herstellungsverfahrens sind Gegenstand der jeweiligen Unteransprüche.The above object is achieved by electrically conductive paper structure according to claim 1 and the process for its preparation according to claim 15. Preferred embodiments of the inventive electrically conductive paper structure and its manufacturing method are the subject of the respective subclaims.

Das erfindungsgemäß elektrisch leitende Papiergefüge weist als wesentliche Materialkomponenten eine Mischung aus Faserstoffen, chemischen Additiven und Restfeuchte auf. Dabei umfasst die Mischung der Faserstoffe wenigstens cellulosehaltige Fasersoffe und Kohlenstofffasern, insbesondere recycelte Kohlenstofffasern, deren Mischungsverhältnis so gewählt ist, dass der spezifische Widerstand des fertigen Papiergefüges unter Standardbedingungen in einem Bereich zwischen 10-1 Ωm und 10-6 Ωm liegt. Im Stand der Technik, wie zum Beispiel in der US 3367851 von Manuel Filreis , ist hingegen nur elektrisch leitendes Papiergefüge bekannt mit einen spezifischen Widerstand zwischen 0,36•10-3 Ωm und 0,6 Ωm.The inventively electrically conductive paper structure has as essential material components a mixture of fibrous materials, chemical additives and residual moisture. In this case, the mixture of fibers comprises at least cellulosic Fasersoffe and carbon fibers, in particular recycled carbon fibers whose mixing ratio is selected so that the specific resistance of the finished paper structure under standard conditions in a range between 10 -1 Ωm and 10 -6 Ωm. In the prior art, such as in the US 3367851 by Manuel Filreis , however, only electrically conductive paper structure is known with a resistivity between 0.36 • 10 -3 Ωm and 0.6 Ωm.

Gemäß der vorliegenden Erfindung werden hierbei als cellulosehaltige Fasersoffe alle Faserstoffe, insbesondere natürlichen Ursprungs verstanden, welche vorzugsweise aus einer Gruppe von Faserstoffen ausgewählt werden, welche Holzfasern, Halbzellstoffe, Thermomechanical Pulp, Hadern bzw. Baumwollfasern, chemisch aufgeschlossene Cellulose wie Sulfat- oder Sulfitzellstoff, Holzstoff, chemisch modifizierten Holzstoff, wiederaufbereiteten Faserstoffe, Kombinationen hiervon und dergleichen umfasst.According to the present invention, cellulosic fibrous materials are understood as meaning all fibrous materials, in particular of natural origin, which are preferably selected from a group of fibrous materials, which are wood fibers, hemicellulars, thermomechanical pulp, rags or cotton fibers, chemically digested cellulose such as sulfate or sulfite pulp, mechanical pulp , chemically modified wood pulp, recycled pulps, combinations thereof, and the like.

Unter Kohlenstofffasern im Sinn der vorliegenden Erfindung werden vorzugsweise industriell erzeugte Fasern, die aus kohlenstoffhaltigem Material gebildet und beispielsweise durch Pyrolyse in ein graphitartig Kohlenstoffanordnung umgewandelt werden verstanden. Solche Fasern können isotrop oder anisotrop erzeugt werden und haben meist einen Durchmesser von etwa 5 µm bis 8 µm. Diese Einzelfasern werden bei der Verarbeitung zu Bündel (Roving) mit 1.000 bis 400.000 Einzelfasern zusammengefasst und können dann weiterverarbeitet werden. Kohlestofffasern sind sowohl elektrisch, als auch thermisch gut leitfähig. Darüber hinaus werden als Kohlenstofffasern Faserstoffe aus einer Gruppe verstanden, welche hochfeste Kohlenstofffasern, insbesondere high tensity / high tenacity, intermediate modulus, hochsteife insbesondere high modulus, ultra modulus, ultra high modulus, ultra modulus strength, hochsteife / hochfeste Kohlenstofffasern, Kombinationen hiervon und dergleichen aufweist.For the purposes of the present invention, carbon fibers are preferably understood as meaning industrially produced fibers which are formed from carbonaceous material and are converted, for example, by pyrolysis, into a graphitic carbon arrangement. Such fibers can be produced isotropically or anisotropically and usually have a diameter of about 5 microns to 8 microns. These single fibers are bundled during processing into bundles (rovings) with 1,000 to 400,000 individual fibers and can then be further processed. Carbon fibers are highly conductive both electrically and thermally. Moreover, carbon fibers are understood to be fibers from a group which are high-strength carbon fibers, in particular high-tensity / high tenacity, intermediate modulus, high modulus, especially high modulus, ultra modulus, ultra high modulus, ultra modulus strength, high stiffness / high strength carbon fibers, combinations thereof and the like having.

In der Industrie finden zunehmend kohlenstofffaserverstärke Kunststoffe (CFK) als Leichtbaumaterial Anwendung. Dieser Wachstumstrend der Vergangenheit wird auch in Zukunft weiter anhalten. CFK setzt sich im Allgemeinen aus einzelnen Kohlefasern, Kohlefaserrovings oder Kohlefasergeweben in Verbindung mit Epoxidharz als Matrix zusammen. Durch die sehr energieintensive Produktion der Kohlefasern stellt sich zunehmend die Frage der Nachhaltigkeit. Da in naher Zukunft mit steigenden Abfallströmen ausgedienter CFK-Produkte zu rechnen ist, sind bereits jetzt Lösungen zur Verwertung dieser Materialien zu entwickeln und bereitzustellen.Carbon fiber reinforced plastics (CFRP) are increasingly being used in industry as a lightweight construction material. This growth trend of the past will continue in the future. CFRP is generally composed of individual carbon fibers, carbon fiber rovings or carbon fiber fabrics in combination with epoxy resin as a matrix. The energy-intensive production of carbon fibers is increasingly raising the question of sustainability. Since in the near future increasing waste streams of disused CFRP products are to be expected, solutions for the recycling of these materials are already to be developed and provided.

Eine mögliche Aufbereitung solcher kohlenstofffaserverstärke Kunststoffe kann beispielsweise durch die thermochemische Spaltung (Pyrolyse) von organischen Verbindungen erfolgen, bei welcher das Epoxidharz aus dem kohlenstofffaserhaltigen Kunststoff entfernt (insbesondere durch Sublimation) wird. Mit diesem Prozess erhält man relativ reine Kohlenstofffasern, welche nach der Zerfaserung, Sortierung und ggf. Zerkleinerung für eine Weiterverarbeitung zur Verfügung stehen.A possible preparation of such carbon fiber-reinforced plastics can be carried out, for example, by the thermochemical cleavage (pyrolysis) of organic compounds, in which the epoxy resin is removed from the carbon-containing plastic (in particular by sublimation). With this process, relatively pure carbon fibers are obtained, which are available for further processing after defibration, sorting and optionally comminution.

Bei der Zerfaserung und Zerkleinerung der freigelegten Kohlenstoffstrukturen liegt es auch im Sinn der vorliegenden Erfindung, dass die so erhaltenen Faserstoffe eine bevorzugte Längenverteilung bzw. einen entsprechenden Schwerpunkt aufweisen, welche vorzugsweise in einem Bereich zwischen 1 µm bis 50.000 µm, vorzugsweise in einem Bereich zwischen 8.000 µm bis 50.000 µm, besonders bevorzugt in einem Bereich zwischen 1 µm bis 8.000 µm und weiter besonders bevorzugt in einem Bereich zwischen 5.000 µm bis 8.000 µm liegt. Diese Längenverteilung ist sowohl beim Einsatz von primären Kohlenstofffasern, als auch bei wiederaufbereiteten Kohlenstofffasern von Vorteil, da sich so die entsprechenden Kohlenstofffasern gut und insbesondere homogen mit den übrigen cellulosehaltigen Faserstoffen des Stallgemisches zur Herstellung des Papiergefüges mischen lassen. Ziel ist es insbesondere hierbei, eine möglichst homogene Verteilung der wenigstens zwei Faserstoffbestandteile sowohl in der Suspension zur Herstellung eines Papiergefüges, als auch im Papiergefüge selbst zu gewährleisten.In the case of defibering and comminution of the exposed carbon structures, it is also within the meaning of the present invention that the fibrous materials thus obtained have a preferred length distribution or a corresponding center of gravity, preferably in a range between 1 μm to 50,000 μm, preferably in a range between 8,000 μm to 50,000 μm, more preferably in a range between 1 μm to 8,000 μm and more preferably in a range between 5,000 μm to 8,000 μm. This length distribution is in both the use of primary carbon fibers, as well as recycled Carbon fibers of advantage, since so can mix the corresponding carbon fibers well and in particular homogeneously with the other cellulose-containing fibers of the stable mixture for the production of the paper structure. The aim in particular is to ensure the most homogeneous possible distribution of the at least two pulp constituents both in the suspension for producing a paper structure and in the paper structure itself.

Gemäß der bevorzugten Ausführungsform der vorliegenden Erfindung ist der Anteil an Kohlenstofffasern in dem Papiergefüge (bei kontrollierten klimatischen Bedingungen von 23 °C und 50 % rel. Luftfeuchtigkeit) größer 35 % bzw. liegt zwischen größer 35 % und 99 %, vorzugsweise zwischen 45 % und 85 %, besonders bevorzugt zwischen 50 % und 80 %, ganz besonders bevorzugt über 50 %. Hierbei ist auch erfindungsgemäß zu berücksichtigen, dass mit der Zunahme des Anteils an primären und/oder wiederaufbereiteten Kohlenstofffasern der spezifische Widerstand des hiermit gebildeten Papiergefüges abnimmt und die Leitfähigkeit des so gebildeten Papiers zunimmt.According to the preferred embodiment of the present invention, the proportion of carbon fibers in the paper structure (at controlled climatic conditions of 23 ° C. and 50% relative atmospheric humidity) is greater than 35% or between greater than 35% and 99%, preferably between 45% and 85%, more preferably between 50% and 80%, most preferably over 50%. It should also be considered according to the invention that with the increase in the proportion of primary and / or recycled carbon fibers, the specific resistance of the paper structure thus formed decreases and the conductivity of the paper thus formed increases.

Vorteil eines erhöhten Anteils an Kohlenstofffasern im Papiergefüge sind unter anderem eine verbesserte Leitfähigkeit, die Reduzierung des elektrischen Widerstandes im Blatt- bzw. Papiergefüge und die damit verbundene höhere Leitungsaufnahme. Erzielt werden kann der erhöhte Einsatz von Kohlenstofffasern durch die gewählte Faserlängenverteilung der Kohlenstofffasern und/oder die Kombination mit dem Papierfaserstoff. Dieser kann beispielsweise Bauwollfaserstoff (Hadern) sein, der insbesondere durch eine gezielte Mahlung (Holländermahlung) gezielt fibrilliert wird und damit ein besonders hohes Festigkeitspotential für das zu erzeugende Papiergefüge bereitstellen kann.The advantage of an increased proportion of carbon fibers in the paper structure are, inter alia, improved conductivity, the reduction of the electrical resistance in the sheet or paper structure and the associated higher line pickup. The increased use of carbon fibers can be achieved by the selected fiber length distribution of the carbon fibers and / or the combination with the paper pulp. This can be, for example, cotton fiber (rags), which is specifically fibrillated in particular by targeted grinding (Holländermahlung) and thus can provide a particularly high strength potential for the paper structure to be produced.

Der spezifische Widerstand des erfindungsgemäßen Papiergefüges liegt im Bereich von 10-2 Ωm und 10-5 Ωm, vorzugsweise zwischen 10-2 und 10-4 Ωm, besonders bevorzugt zwischen 10-2 bis 10-3 Ωm, ganz besonders bevorzugt bei ca. 30-2 Ωm bzw. 50-2 Ωm.The specific resistance of the paper structure according to the invention is in the range of 10 -2 Ωm and 10 -5 Ωm, preferably between 10 -2 and 10 -4 Ωm, more preferably between 10 -2 to 10 -3 Ωm, most preferably at about 30 -2 Ωm and 50 -2 Ωm, respectively.

Entsprechend einer weiteren, besonders bevorzugten Ausführungsform der vorliegenden Erfindung wird das oder die chemischen Additive aus einer Gruppe ausgewählt werden, welche insbesondere Retentionsmittel, Entwässerungshilfsmittel, Retentionsmittel-Dual-Systeme oder Mikropartikelsysteme,According to a further, particularly preferred embodiment of the present invention, the chemical additive (s) will be selected from a group which in particular comprises retention aids, drainage aids, retention agent dual systems or microparticle systems,

Nass- und Trockenverrestiger, Leimungsmittel, Fullstoffe und/ oder Pigmente, insbesondere aus einer Gruppe von Talkum, Titandioxid, Aluminiumhydroxid, Bentonit, Bariumsulfat, Calciumcarbonat, Kaolin ausgewählt, Entschäumer, Entlüfter, Biozide, Enzyme, Bleichhilfsmittel, optische Aufheller, Farbstoffe, Nuancierfarbstoffen, Störstofffänger, Fällungsmittel (Fixiermittel), Benetzungsmittel, pH-Regulatoren umfasst.Wet and dry residues, sizing agents, fillers and / or pigments, in particular selected from a group of talc, titanium dioxide, aluminum hydroxide, bentonite, barium sulfate, calcium carbonate, kaolin, defoamers, deaerators, biocides, enzymes, bleaching aids, optical brighteners, dyes, shading dyes, Contaminant catcher, precipitating agent (fixer), wetting agent, pH regulators.

Alternativ oder in Kombination kann das chemische Additiv auch aus einer Gruppe von vorzugsweise wasserlöslichen Polymeren ausgewählt werden, welche insbesondere aminhaltige Polymere, Polyethylenimin, Pyrolidin, Polyamide, Polyacrylamid, Aridin, Proteine, Peptide, polyetherhaltige Polymere, insbesondere Polyethylenoxid, Polyether, hydroxylgruppenhaltige Polymere, insbesondere Stärke, Carboxymethylcellulose, Polyvinylalkohol, geladene Polymere, insbesondere kationische Polymere, insbesondere kationische Stärke, Maisstärke, Kartoffelstärke, Weizenstärke, Reisstärke, ammoniumgruppenhaltige Polymere, anionische Polymere, insbesondere anionisch modifizierte Polyacrylamide, sulfonisierte Polymere, anorganische Salze mit hoher Ladungsdichte, insbesondere Aluminiumsalze, Aluminium(III)Chloride, Aluminiumsulfat, Natriumaluminat, anorganische, geladene Partikel/ Pigmente, insbesondere Bentonit, Montmorillonit, Natriumsilikat, Naßverfestiger, insbesondere Epichlorhydrinharze, Glyoxal, Zirkoniumsalze, Zirkoncarbonat, Kombination aus anionischen Polymeren und kationisch modifiziertem Pigmenten, Hilfsmittel zur Reduzierung des Entflammpunktes, Kombinationen hiervon und dergleichen umfasst.Alternatively or in combination, the chemical additive can also be selected from a group of preferably water-soluble polymers which in particular amine-containing polymers, polyethyleneimine, pyrolidine, polyamides, polyacrylamide, aridine, proteins, peptides, polyether-containing polymers, in particular polyethylene oxide, polyether, hydroxyl-containing polymers, in particular Starch, carboxymethylcellulose, polyvinyl alcohol, charged polymers, in particular cationic polymers, in particular cationic starch, corn starch, potato starch, wheat starch, rice starch, polymers containing ammonium groups, anionic polymers, in particular anionically modified polyacrylamides, sulphonated polymers, inorganic salts with high charge density, in particular aluminum salts, aluminum ( III) chlorides, aluminum sulfate, sodium aluminate, inorganic charged particles / pigments, in particular bentonite, montmorillonite, sodium silicate, wet strength agent, especially epichlorohydrin resins, glyoxal, Zi rkoniumsalze, zirconium carbonate, combination of anionic polymers and cationically modified pigments, aids for reducing the flash point, combinations thereof, and the like.

Das erfindungsgemäße Papiergefüge weist gemäß einer weiteren besonders bevorzugten Ausführungsform ein Flächengewicht nach DIN EN ISO 536 auf, welches in einem Bereich von 15 g/m2 bis 1.000 g/m2, vorzugsweise zwischen 20 g/m2 bis 800 g/m2, besonders bevorzugt zwischen 20 g/m2 bis 300 g/m2, ganz besonders bevorzugt über 40 g/m2 liegt.According to a further particularly preferred embodiment, the paper structure according to the invention has a basis weight according to DIN EN ISO 536 which is in the range from 15 g / m 2 to 1,000 g / m 2 , preferably from 20 g / m 2 to 800 g / m 2 , more preferably between 20 g / m 2 to 300 g / m 2 , very particularly preferably above 40 g / m 2 .

Ein solches Papiergefüge weist ferner wenigstens in Abhängigkeit der Einsatzmenge von Kohlenstofffasern eine Leistungsaufnahme auf, welche im Bereich von 50 W/m2 bis 5.000 W/m2, vorzugsweise eine im Bereich von 100 W/m2 bis 3.700 W/m2, besonders bevorzugt im Bereich von 100 W/m2 bis 1.000 W/m2, ganz besonders bevorzugt im Bereich von 250 W/m2 bis 750 W/m2 liegt. Hierbei ist auf der Oberfläche des Papiergefüges eine Temperatur im Bereich von 15 °C bis 130 °C, vorzugsweise eine Oberflächentemperatur im Bereich von 35 °C bis 100 °C, besonders bevorzugt eine Oberflächentemperatur im Bereich von 15 °C bis 99 °C, ganz besonders bevorzugt eine Oberflächentemperatur im Bereich von 75 °C bis 130 °C zu erzielen.Such a paper structure furthermore has a power consumption, at least as a function of the amount of carbon fiber used, which is in the range from 50 W / m 2 to 5,000 W / m 2 , preferably in the range from 100 W / m 2 to 3,700 W / m 2 preferably in the range from 100 W / m 2 to 1000 W / m 2 , very particularly preferably in the range from 250 W / m 2 to 750 W / m 2 . Here, on the surface of the paper structure, a temperature in the range of 15 ° C to 130 ° C, preferably a surface temperature in the range of 35 ° C to 100 ° C, more preferably a surface temperature in the range of 15 ° C to 99 ° C, most preferably a surface temperature in the range of 75 ° C to 130 ° C to achieve.

Die vorliegende Erfindung wird auch durch ein Verfahren zur Herstellung des entsprechenden Papiergefüges und dessen Verwendung zur Herstellung spezifischer Produkte gelöst.The present invention is also achieved by a method for producing the corresponding paper structure and its use for producing specific products.

Hierbei weist das Verfahren zur Herstellung eines elektrisch leitenden Papiergefüges wenigstens folgende Schritte auf:

  • Bereitstellen einer Stoffsuspension aus cellulosehaltigem Faserstoff und Wasser;
  • Zugabe wenigstens eines chemischen Additives;
  • Zugabe der Kohlenstofffasern;
  • Entwässern der Stoffsuspension und Herstellung des Papiergefüges;
  • Mechanische Entwässerung und Trocknung des elektrisch leitenden Papiergefüges.
In this case, the method for producing an electrically conductive paper structure has at least the following steps:
  • Providing a stock suspension of cellulose-containing pulp and water;
  • Adding at least one chemical additive;
  • Adding the carbon fibers;
  • Dewatering the stock suspension and making the paper structure;
  • Mechanical dewatering and drying of the electrically conductive paper structure.

Gemäß einem weiteren alternativen Ausführungsbeispiel ist wenigstens ein Anteil der Kohlenstofffasern wiederaufbereitete Kohlenstofffasern, bei welchen beispielsweise eine pyrolytische Aufbereitung der Kohlefaserverbundwerkstoffe mit Harzentfernung durch Sublimation verwendet wurde. Solche wiederaufbereitete Kohlenstofffasern können Kohlefaserabschnitte oder aber auch Kohlefaserverbundwerkstoffe wie beispielsweise Rovingreste sein. Darüber hinaus ist es von besonderem Vorteil, dass die Faserlängenverteilung der wiederaufbereiteten Kohlenstofffasern mittels einer Zerkleinerungsstufe erfolgt.According to another alternative embodiment, at least a portion of the carbon fibers are recycled carbon fibers using, for example, pyrolytic treatment of the carbon fiber composites with resin removal by sublimation. Such recycled carbon fibers may be carbon fiber sections or even carbon fiber composites such as roving residues. In addition, it is of particular advantage that the fiber length distribution of the recycled carbon fibers takes place by means of a comminution stage.

Die Erfindung umfasst ferner auch die Verwendung des elektrisch leitenden Papiergefüges als Heizpapier, insbesondere als Heizelement in Böden, Wänden, Tapeten, Behältnissen, Stoffen, Kleidung, Tischplatten, Heizplatten, Heizmatten, Auto-Innenheizungen, insbesondere Tür-, Sitz-, Armaturenbrettheizungen, dem Strahlenschutz, Kombinationen hiervon und dergleichen.The invention further includes the use of the electrically conductive paper structure as a heating paper, in particular as a heating element in floors, walls, wallpaper, containers, fabrics, clothing, table tops, hot plates, heating mats, car interior heaters, especially door, seat, dashboard heaters, the Radiation protection, combinations thereof and the like.

Gemäß einem weiteren, besonders bevorzugten Ausführungsbeispiels ist das erfindungsgemäß elektrisch leitende Papiergefüge auch dazu geeignet, neben der stromleitenden Funktion auch insbesondere für die Abschirmung von Strahlung, wie zum Beispiel elektromagnetischer Strahlung verwendet zu werden.According to a further, particularly preferred embodiment, the electrically conductive paper structure according to the invention is also suitable, in addition to electrically conductive function also to be used in particular for the shielding of radiation, such as electromagnetic radiation.

Im Rahmen von Untersuchungen konnte hierbei gezeigt werden, dass zum Beispiel elektromagnetische Strahlung, insbesondere Mikrowellenstrahlung durch den Einsatz des erfindungsgemäßen Papiergefüges deutlich abgeschirmt werden kann.In the course of investigations, it was possible to show that, for example, electromagnetic radiation, in particular microwave radiation, can be clearly shielded by the use of the paper structure according to the invention.

Erfindungsgemäß elektrisch leitende Papiergefüge können somit in technischen Anlagen, bei elektronischen Baugruppen, in Wohnräumen und vielen anderen Anwendungen eingesetzt werden, um elektromagnetische Strahlung wirksam zu unterdrücken und somit abschirmend zu wirken. Ebenfalls kann es zum Einsatz kommen, um Menschen und Tiere gegenüber elektrischen, magnetischen und elektromagnetischen Feldern zu schützen.According to the invention, electrically conductive paper structures can thus be used in technical installations, in electronic assemblies, in living spaces and in many other applications in order to effectively suppress electromagnetic radiation and thus have a shielding effect. It can also be used to protect people and animals against electrical, magnetic and electromagnetic fields.

Bei technischer Betrachtung kann die Zuverlässigkeit und Funktionssicherheit von empfindlichen Geräten und Einrichtungen verbessert werden. Somit können erfindungsgemäß elektrisch leitende Papiergefüge den Strahlungsextinktionskoeffizienten stark beeinflussen bzw. zu Gunsten der Umwelt verändern.From a technical point of view, the reliability and reliability of sensitive equipment and facilities can be improved. Thus, according to the invention, electrically conductive paper structures can strongly influence the radiation extinction coefficient or change it in favor of the environment.

Ein weiterer Vorteil des erfindungsgemäßen elektrisch leitenden Papiergefüges ist, dass die Aufarbeitung eines Kohlefaserverbundwerkstoffes, wie insbesondere CFK pyrolytisch erfolgt, wobei man das Harz durch Sublimation unter einer Temperatur von 550 °C entfernt - und somit die Kohlenstofffaser schadensfrei freigelegt wird. Hierbei liegen in der Regel uneinheitliche Faserlängen vor. Mittels einer nachgeschaltenen Zerkleinerungsstufe werden diese Fasern homogenisiert und auf einen definierten Längenbereich gebracht. Die in verschiedenen Formen und Größen pyrolisierten und aufbereiteten Kohlenstofffasern werden in der Stoffaufbereitung mit der Altpapiersuspension gemischt und dann gemeinsam dem flächigen Papierherstellungsprozess zugeführt.Another advantage of the electrically conductive paper structure according to the invention is that the workup of a carbon fiber composite material, in particular CFK is pyrolytic, wherein the resin is removed by sublimation at a temperature of 550 ° C - and thus the carbon fiber is exposed without damage. As a rule, uneven fiber lengths are present. By means of a downstream comminution stage, these fibers are homogenized and brought to a defined length range. The carbon fibers, which are pyrolyzed and prepared in various shapes and sizes, are mixed in the stock preparation with the waste paper suspension and then fed together to the two-dimensional papermaking process.

Als weiterer Vorteil des erfindungsgemäßen Papiergefüges ist anzuführen, dass das Papiergefüge relativ kostengünstig hergestellt werden kann, den Einsatz von Recyclingfasern sowohl bzgl. der Kohlenstofffasern als auch der Cellulosefasern ermöglicht, das Papiergefüge eine hohe Flexibilität / Verformbarkeit bereitstellt (Beweglichkeit), das Papiergefüge auch mit niedriger flächenbezogener Masse herstellbar ist, einfach in der Handhabung (Verwendung) und problemlose in der Lagerhaltung ist und sich auch einfach und spezifisch Ausrüsten lässt.A further advantage of the paper structure according to the invention is that the paper structure can be produced relatively inexpensively, the use of recycled fibers both with respect to the carbon fibers and the cellulose fibers allows the paper structure provides a high flexibility / malleability (mobility), the paper texture with lower area related mass is easy to handle, easy to use and easy to store, and also easy and specific to equip.

Durch die Flexibilität des Materials kann nahezu jede Form - wie mit normalem Papier - gestaltet werden.Due to the flexibility of the material almost any shape can be designed - as with normal paper.

Die Verarbeitung der Recycling-Kohlefaser (auch "rC" genannt) erfolgt zu dem erfindungsgemäßen elektrisch leitenden Papiergefüge mit einem Anteil von 1 bis zu 99 % der entsprechenden Recycling-Kohlefaser aus einer Faserstoffsuspension im Papierherstellungsprozess zu einem Papierblatt. Die flächenbezogene Masse kann hierbei zwischen 20 g/m2 und 1.000 g/m2 liegen.The processing of the recycled carbon fiber (also called "rC") takes place to the inventive electrically conductive paper structure with a proportion of 1 to 99% of the corresponding recycled carbon fiber from a pulp suspension in the papermaking process to a paper sheet. The basis weight may be between 20 g / m 2 and 1,000 g / m 2 .

Das kohlefaserhaltige Papiergefüge kann erfindungsgemäß elektrifiziert werden. Dabei erfolgt die Elektrifizierung zum Beispiel mit Schwachstrom zwischen 12 V und 40 V, bevorzugt mit 12 V oder 24 V (Gleich-, Wechselstrom), wodurch das kohlefaserhaltige Papiergefüge als Heizfläche verwendet werden kann.The carbon fiber-containing paper structure can be electrified according to the invention. The electrification is carried out, for example, with a low current between 12 V and 40 V, preferably with 12 V or 24 V (DC, AC), whereby the carbon fiber-containing paper structure can be used as a heating surface.

Versuche zeigen, dass zum Beispiel bei 50 - 80 %-igen Kohlenfaserstoffanteil im Papiergefüge in Abhängigkeit der Stromaufnahme eine Oberflächentemperatur zwischen 15 bzw. 35 - 80 °C erreicht werden kann. Durch Anlegen eines höheren elektrischen Stromes ist es auch möglich, die Oberflächentemperatur auf über 100 °C zu steigern. Hierbei sind aber ggf. aufgrund des Entflammpunktes von Papier ggf. weitere Maßnahmen zu ergreifen, um insbesondere eine Entzündung des Papiergefüges im Betrieb als Heizelement zu verhindern. Hierzu kann beispielsweise das Papiergefüge mit entflammungshemmenden Hilfsstoffen ausgerüstet oder behandelt werden, um somit die entsprechende Eigenschaft bereit zu stellen.Experiments show that, for example, at 50-80% carbon fiber content in the paper structure, depending on the power consumption, a surface temperature between 15 and 35 - 80 ° C can be achieved. By applying a higher electric current, it is also possible to increase the surface temperature to over 100 ° C. In this case, however, if necessary, due to the firing point of paper, further measures may have to be taken, in particular to prevent inflammation of the paper structure during operation as a heating element. For this purpose, for example, the paper structure can be equipped or treated with flame-retardant auxiliaries, in order thus to provide the corresponding property.

Ein möglicher Vorteil eines solchen Papiergefüges, welches ggf. auch als "Heizpapier" bezeichnet werden kann liegt u.a. darin, dass das Material den Papiercharakter beibehält, weiterhin geschmeidig bleibt und wie klassisches Papier in alle Formen gestaltet und beschnitten werden kann. Ein Kaschieren auf Stein, Textilien oder andere Materialien ist ebenfalls möglich. So kann ein entsprechendes Papiergefüge als Wandheizung eingesetzt werden und durch die Anordnung an kalten Wänden wie beispielsweise in Kellern zur Vermeidung von Kältebrücken beitragen. Hierbei ist es nicht von Nöten besonders hohe Oberflächentemperaturen bereit zu stellen, sondern es ist ausreichend das Papiergefüge auf Raumtemperatur zu erwärmen. Damit kann bereits die Bildung von feuchten Stellen und somit auch die Gefahr von Schimmelbildung deutlich reduziert werden.A possible advantage of such a paper structure, which may possibly also be referred to as "heating paper" is, inter alia, that the material retains the paper character, remains supple and how classic paper can be shaped and trimmed in all forms. Laminating on stone, textiles or other materials is also possible. Thus, a corresponding paper structure can be used as a wall heating and contribute by the arrangement on cold walls such as basements to avoid cold spots. It is not necessary to provide particularly high surface temperatures, but it is sufficient the paper texture to room temperature to warm up. Thus, the formation of moist spots and thus the risk of mold growth can be significantly reduced.

Darüber hinaus ist es von Vorteil, dass bei diesem System durch die flächige Ausdehnung und Homogenität eine gleichmäßige und flächige Wärmeverteilung bereit gestellt werden kann. Wird das Papiergefüge durch Löcher oder Risse beschädigt, so leidet die Stromführung bzw. Leitfähigkeit nicht, die gleichmäßige Verteilung der Wärme wird beibehalten.In addition, it is advantageous that in this system by the flat expansion and homogeneity a uniform and areal heat distribution can be provided. If the paper texture is damaged by holes or cracks, the current conduction or conductivity does not suffer, the uniform distribution of heat is maintained.

Die Messung der Widerstandswerte erfolgte mit einem LCR-Messgerät des Herstellers Hewlett Packard. Die Messspannung zur Widerstandsbestimmung betrug 3 V. Die Messzelle wies einen kreisförmigen Zentrumskontakt und einen ringförmigen Außenkontakt im gleichmäßigen Abstand von 1 cm zum Zentrum auf.The measurement of the resistance values took place with an LCR measuring device of the manufacturer Hewlett Packard. The measuring voltage for determining resistance was 3 V. The measuring cell had a circular center contact and an annular external contact at a uniform distance of 1 cm from the center.

Nachfolgend wird die Erfindung anhand verschiedener Ausführungsbeispiele beschrieben, wobei darauf hingewiesen wird, dass die Erfindung nicht auf die hier dargestellte Ausführungen beschränkt, sondern vielmehr auch entsprechende Abwandlungen im Sinne der vorliegenden Erfindung sind. Weitere Merkmale der Erfindung ergeben sich aus der nachfolgenden detaillierten Beschreibung der Zeichnungen in Verbindung mit den Ansprüchen. Es zeigt:

  • Figuren 1 bis 3 fotographische Aufsichtsdarstellungen verschiedener Ausführungsbeispiele des erfindungsgemäßen elektrisch leitendes Papiergefüge mit recycelten Kohlenstofffasern;
  • Figur 4 eine graphische Darstellung der Entwicklung der Papierfestigkeit des Papiergefüges bei Zunahme des Kohlenstofffaseranteils;
  • Figuren 5 und 6 graphische Darstellungen der Temperaturentwicklung des Papiergefüges über die Zeit;
  • Figur 7 eine graphische Darstellung der Leistungsaufnahme des Papiergefüges in Abhängigkeit der Oberflächentemperatur;
  • Figuren 8 und 9 graphische Darstellungen des elektrischen Widerstandes in Abhängigkeit der Oberflächentemperatur.
The invention will be described with reference to various embodiments, wherein it should be noted that the invention is not limited to the embodiments shown here, but rather are also corresponding modifications in the context of the present invention. Further features of the invention will become apparent from the following detailed description of the drawings in conjunction with the claims. It shows:
  • FIGS. 1 to 3 photographic top views of various embodiments of the invention electrically conductive paper structure with recycled carbon fibers;
  • FIG. 4 a graph of the development of the paper strength of the paper structure with increasing carbon fiber content;
  • Figures 5 and 6 graphical representations of the temperature development of the paper structure over time;
  • FIG. 7 a graphical representation of the power consumption of the paper texture as a function of the surface temperature;
  • FIGS. 8 and 9 graphical representations of the electrical resistance as a function of the surface temperature.

In den Figuren 1 bis 3 sind fotographische Aufsichtdarstellung des erfindungsgemäßen elektrisch leitenden Papiergefüges mit recycelten Kohlenstofffasern dargestellt. Gut erkennbar sind im Kontrast zu dem hier verwendeten altpapierhaltigen Papierfaserstoff die Anordnung der stabförmigen, dunkel bis schwarzfarbigen recycelten Kohlenstofffasern in dem Papiergefüge.In the FIGS. 1 to 3 are shown a top plan photograph of the inventive electrically conductive paper structure with recycled carbon fibers. The arrangement of the rod-shaped, dark to black-colored recycled carbon fibers in the paper structure are clearly recognizable in contrast to the wastepaper-containing paper pulp used here.

In Figur 4 ist graphische die Entwicklung der Papierfestigkeit des Papiergefüges in Abhängigkeit des Kohlenstofffaseranteils im Papiergefüge dargestellt. Dabei ist auf der Abszisse der Anteil an recycelten Kohlestofffasern im Papiergefüge in Stufen von 0, 20, 50 und 80% und auf der Ordinate die Festigkeit ausgehend von 100 % ohne einen Kohlenstofffaseranteil aufgetragen. Man sieht deutlich, wie die Festigkeit mit Zunahme an Kohlenstofffasern abnimmt und bei 80 % Anteil an Kohlenstofffasern nur noch ca. 30 % des Ausgangswertes beträgt.In FIG. 4 Graphical is the development of the paper strength of the paper structure as a function of the carbon fiber content in the paper structure. The abscissa represents the proportion of recycled carbon fibers in the paper structure in steps of 0, 20, 50 and 80% and the ordinate indicates the strength starting from 100% without a carbon fiber fraction. It can be seen clearly how the strength decreases with an increase in carbon fibers and, with an 80% share of carbon fibers, only about 30% of the initial value.

In den Figuren 5 und 6 ist jeweils graphische die Oberflächentemperaturentwicklung (Ordinate) verschiedener Papiergefüge über die Zeit (Abszisse) dargestellt. Hierbei wurden unterschiedliche Papiergefüge untersucht und die Oberflächentemperatur über 60 Sekunden (Figur 5) und 120 Sekunden (Figur 6) erfasst.In the Figures 5 and 6 Graphical surface temperature evolution (ordinate) of various paper structures over time (abscissa) is shown. Different paper structures were examined and the surface temperature exceeded 60 seconds ( FIG. 5 ) and 120 seconds ( FIG. 6 ) detected.

In der Figur 7 ist graphische die Leistungsaufnahme eines Papiergefüges pro Quadratmeter (Pspez. in W/m2) in Abhängigkeit der Oberflächentemperatur in °C dargestellt. Hierbei wird deutlich wie stark die Leistungsaufnahme ausgehend bei 26,6 °C mit ca. 100 W/m2 auf über 400 W/m2 bei 40,0 °C steigt. Dabei wurde eine Spannung von 12 V bei einer Stromstärke von 2 A an den gegenüberliegenden Kanten des Papiergefüges angelegt.In the FIG. 7 is the graphical representation of the power consumption of a paper structure per square meter (P spec in W / m 2 ) as a function of the surface temperature in ° C. Here, it becomes clear how much the power consumption, starting at 26.6 ° C with about 100 W / m 2 to more than 400 W / m 2 at 40.0 ° C increases. In this case, a voltage of 12 V was applied at a current of 2 A at the opposite edges of the paper structure.

Schließlich zeigen die Figuren 8 und 9 die Entwicklung des elektrischen Widerstandes in Ohm in Abhängigkeit der Oberflächentemperatur in °C. In beiden Darstellungen wird deutlich, dass mit steigender Oberflächentemperatur - hier um ca. 20°C - der Widerstand des Papiergefüges um ca. 20 % abnimmt.Finally, the show FIGS. 8 and 9 the development of the electrical resistance in ohms as a function of the surface temperature in ° C. In both representations it becomes clear that with increasing surface temperature - here by approx. 20 ° C - the resistance of the paper structure decreases by approx. 20%.

Im Rahmen von Untersuchungen zur Abschirmungseignung des erfindungsgemäßen Papiergefüges wurde festgestellt, dass zum Beispiel Mikrowellenstrahlung (Frequenz ca. 2450 MHz) durch ein entsprechendes Papiergefüge um mehr als 95 % reduziert werden konnte. So lag die Leistung der Quelle bei ca. 8 mW/cm2 und hinter dem Papiergefüge bei 0,4 mW/cm2.As part of investigations into Abschirmungsignung the paper structure of the invention was found that, for example, microwave radiation (frequency about 2450 MHz) could be reduced by a corresponding paper texture by more than 95%. The power of the source was about 8 mW / cm 2 and behind the paper structure at 0.4 mW / cm 2 .

Nachfolgend wird die Verarbeitung des erfindungsgemäßen Papier- / Blattgefüges beschrieben.The processing of the paper / sheet structure of the present invention will be described below.

In einem ersten Versuch wurde ein Vließ aus Kohlenstofffasern verarbeitet. An den Seitenrändern wurde das Material gefaltet und in die Faltungen wurden mit einem schwarzen (rußhaltigen) Kleber silberfarbene Drähte eingeklebt.In a first experiment, a fleece made of carbon fibers was processed. The material was folded on the side edges and silver-colored wires were glued into the folds with a black (sooty) adhesive.

Das zweite Vließ bestand auch aus Kohlefaser. An den Seitenrändern wurde das Material ebenfalls gefaltet und in die Faltungen wurden mit einem schwarzen (rußhaltigen) Kleber Kupferdrähte eingeklebt.The second fleece was also made of carbon fiber. The material was also folded at the side edges and copper wires were glued into the folds with a black (sooty) glue.

Im dritten Versuch bestand das Gewebe aus einer Mischung von Kohlenstofffasern und nicht elektrisch leitenden Fasern. An den Seitenrändern wurde das Material wieder gefaltet und in die Faltungen wurden mit einem schwarzen (rußhaltigen) Kleber Kupferdrähte eingeklebt.In the third experiment, the fabric consisted of a mixture of carbon fibers and non-electrically conductive fibers. The material was refolded at the side edges and copper wires were glued into the folds with a black (sooty) glue.

Die Gewebe wurden mit CapaColl GK auf einer Gipskartonplatte verklebt. Anschließend wurde mit Haftgrund grundiert und einmal mit Alpinaweiß beschichtet.The fabrics were glued to a plasterboard with CapaColl GK. It was then primed with primer and once coated with Alpina white.

Das Gewebe aus dem ersten Versuch ließ sich nur unter Schwierigkeiten kleben. Durch die Verklebung und die eingebetteten Drähte verzog sich das Gewebe und haftete nicht richtig auf der Gipskartonplatte - es bildeten sich Wellen, die öfter angedrückt werden mussten, bis der Kleber schließlich soweit abgebunden war, um das Gewebe von sich aus an der Platte haften zu lassen. Durch die Faltung/Verklebung bildeten sich unregelmäßige Kanten auf der Platte. Bei der weiteren Verarbeitung zeigte sich, dass das Gewebe vom Zusammenhalt schwach ist. Malerkrepp ließ sich nicht zerstörungsfrei ablösen. Ansonsten gestaltete sich der weitere Aufbau (Grundieren/Beschichten) als unproblematisch. Die Faltung/Verklebung verursacht eine stark unterschiedliche Schichtdicke im Bereich des Gewebes. Der verwendete Kleber verursacht aber keine Probleme bezüglich der Saugkraft des Untergrundes.The fabric of the first experiment was difficult to glue. As a result of the bonding and the embedded wires, the fabric warped and did not adhere properly to the plasterboard - waves formed, which needed to be pressed more often, until the adhesive finally set sufficiently to adhere the fabric to the panel on its own accord , The folding / gluing formed irregular edges on the plate. Upon further processing, the fabric was weak from cohesion. Malerkrepp could not be detached without destroying it. Otherwise, the further construction (priming / coating) was unproblematic. The folding / gluing causes a very different layer thickness in the area of the tissue. However, the adhesive used does not cause any problems with respect to the suction power of the substrate.

Das Gewebe aus dem zweiten Versuch ließ sich auch nur unter Schwierigkeiten kleben. Durch die Verklebung und die eingebetteten Drähte verzog sich das Gewebe und haftete nicht richtig auf der Gipskartonplatte - es bildeten sich Wellen, die öfter angedrückt werden mussten, bis der Kleber schließlich soweit abgebunden war, um das Gewebe von sich aus an der Platte haften zu lassen. Durch die Faltung/Verklebung bildeten sich unregelmäßige Kanten auf der Platte. Bei der weiteren Verarbeitung zeigte sich, dass das Gewebe des zweiten Versuchs vom Zusammenhalt her zwar schwach ist, es ist allerdings stärker als das Gewebe des ersten Versuchs. Das Malerkrepp ließ sich besser ablösen, als im Versuch 1. Ansonsten gestaltete sich der weitere Aufbau (Grundieren/Beschichten) als unproblematisch. Die Faltung/Verklebung verursacht eine stark unterschiedliche Schichtdicke im Bereich des Gewebes. Dieser Ansatz ist deutlich zu sehen. Der verwendete Kleber verursacht aber keine Probleme bezüglich der Saugkraft des Untergrundes. Im Betrieb erwärmten sich die seitlichen Leiterbahnen überproportional und sehr schnell. Das Vließ wurde mit einer Spannung von 20 - 30 V bestromt.The fabric from the second experiment could be stuck even with difficulty. As a result of the bonding and the embedded wires, the fabric warped and did not adhere properly to the plasterboard - waves formed, which had to be pressed more often, until the adhesive had finally set so far to adhere the tissue to the plate by itself. The folding / gluing formed irregular edges on the plate. Upon further processing, it was found that the tissue of the second experiment is cohesively weak, but it is stronger than the tissue of the first experiment. The painter's crepe peeled off better than in experiment 1. Otherwise, the further structure (priming / coating) was unproblematic. The folding / gluing causes a very different layer thickness in the area of the tissue. This approach is clearly visible. However, the adhesive used does not cause any problems with respect to the suction power of the substrate. During operation, the lateral tracks heated disproportionately and very quickly. The fleece was energized with a voltage of 20-30 V.

Das Gewebe des Versuchs drei ließ sich problemlos verarbeiten, reagierte gut auf den Kleber und haftete gut an der GKP. Durch die Faltung/Verklebung bildeten sich leicht unregelmäßige Kanten auf der Platte. Die weitere Verarbeitung gestaltete sich unproblematisch. Im Gegensatz zu dem Gewebe aus den Versuchen eins und zwei ließ sich das Malerkrepp am besten entfernen. Die Faltung/Verklebung verursacht eine unterschiedliche Schichtdicke im Bereich des Gewebes. Der verwendete Kleber verursacht aber keine Probleme bezüglich der Saugkraft des Untergrundes. Im Betrieb erwärmten sich die seitlichen Leiterbahnen überproportional und sehr schnell. Das Papiergefüge / Vließ wurde mit einer Spannung von 20 - 30 V bestromt.The fabric of Trial Three was easily processed, reacted well to the adhesive, and adhered well to the GKP. By folding / gluing slightly irregular edges formed on the plate. The further processing was unproblematic. In contrast to the tissue from trials one and two, the painter's crepe was best removed. The folding / gluing causes a different layer thickness in the area of the tissue. However, the adhesive used does not cause any problems with respect to the suction power of the substrate. During operation, the lateral tracks heated disproportionately and very quickly. The paper structure / fleece was supplied with a voltage of 20-30 V.

Ein weiterer Versuch mit an den gegenüberliegenden Papierrändern aufgeklebten Kupferfolien zeigten sich sehr zufriedenstellende Ergebnisse hinsichtlich Stromleitung, Strom- und Wärmeverteilung über die gesamte Fläche. Hierbei erwärmten sich die seitlichen Leitbahnen nicht mehr überproportional, sondern wiesen die gleiche Temperatur auf, wie die gesamte Papierfläche.Another trial with copper foils adhered to the opposite paper edges showed very satisfactory results in terms of power conduction, current and heat distribution over the entire area. Here, the side channels no longer heated disproportionately, but had the same temperature as the entire paper surface.

Claims (15)

  1. An electrically conductive paper fabric comprising fiber materials, chemical additives and residual moisture,
    characterized in that
    the paper fabric includes cellulose-containing fiber materials and carbon fibers, due to the mixing ratio of which the specific resistance of the paper fabric is in a range between 10-1 Ωm and 10-6 Ωm,
    wherein the content of carbon fibers is more than 35% or between more than 35% and 99%, preferably between 45% and 85%, particularly preferably between 50% and 80%, further particularly preferably more than 50%, and
    the carbon fibers have a fiber length in a range between 1µm to 50000µm, preferably in a range between 8000µm to 50000µm, particularly preferably in a range between 1µm to 8000µm and further particularly preferably in a range between 5000µm to 8000µm.
  2. The paper fabric of claim 1, characterized in that
    the cellulose-containing fiber material content is selected from a group of fiber materials including wood fibers, semichemical pulp, thermomechanical pulp, rags, chemically pulped cellulose such as sulfate pulp or sulfite pulp, wood pulp, chemically modified wood pulp, recycled fiber materials, combinations thereof and the like.
  3. The paper fabric of any preceding claim, characterized in that
    the chemical additives are selected from a group including, in particular, retention agents, auxiliary dewatering agents, retention agent dual systems or microparticle systems, wet-strength agents and dry-strength agents, sizing agents, fillers and/or pigments, particularly selected from a group of talcum, titanium dioxide, aluminum hydroxide, bentonite, barium sulfate, sodium carbonate, kaolin; defoaming agents, de-airing agents, biocides, enzymes, auxiliary bleaching agents, optical brighteners, colorants, shading dyes, fixatives, precipitating agents (fixing agents), wetting agents, pH regulators, and/or water soluble polymers, particularly amine-containing polymers, polyethylenimine, pyrrolidine, polyamides, polyacrylamide, acridine, proteins, peptides, polyether-containing polymers, particularly polyethylene oxide, polyether, hydroxyl-group containing polymers, particularly starch, carboxymethyl cellulose, polyvinyl alcohol, charged polymers, particularly cationic polymers, particularly cationic starch, corn starch, potato starch, wheat starch, rice starch, ammonium-group containing polymers, anionic polymers, particularly anionically modified polyacrylamides, sulfonated polymers, inorganic salts with high charge density, particularly aluminum salts, aluminum(III) chlorides, aluminum sulfate, sodium aluminate, inorganic charged particles/pigments, particularly bentonite, montmorillonite, sodium silicate, wet-strength agents, particularly epichlorhydrin resins, glyoxal, zirconium salts, zirconium carbonate, combinations of anionic polymers and cationically modified pigments, combinations thereof and the like.
  4. The paper fabric of any preceding claim, characterized in that
    the carbon fibers are selected from a group including high-tensile carbon fibers, particularly high-density / high-tenacity, intermediate-modulus carbon fibers, highly rigid, particularly high-modulus, ultra-modulus, ultra-high modulus, ultra-modulus strength, highly rigid / high-tensile carbon fibers, combinations thereof and the like.
  5. The paper fabric of any preceding claim, characterized in that
    at least part of the carbon fibers are recycled carbon fibers.
  6. The paper fabric of any preceding claim, characterized in that
    the recycled carbon fibers are produced by pyrolytic processing of carbon fiber composite materials including deresination by sublimation.
  7. The paper fabric of any preceding claim, characterized in that
    the recycled carbon fibers are set, in a size-reduction stage, to a homogenous fiber length in a range between 1µm to 50000µm, preferably in a range between 8000µm to 50000µm, particularly preferably in a range between 1µm to 8000µm and further particularly preferably in a range between 5000µm to 8000µm.
  8. The paperfabric of any preceding claim, characterized in that
    the specific resistance of the paper fabric is in a range between 10-2 Ωm and 10-5 Ωm, preferably between 10-2 and 10-4 Ωm, particularly preferably between 10-2 to 10-3 Ωm.
  9. The paper fabric of any preceding claim, characterized in that
    the grammage of the paper fabric according to DIN EN ISO 536 is in a range of 15 to 1000 g/m2, preferably between 20 to 800 g/m2, particularly preferably between 20 to 300 g/m2, further particularly preferably more than 40 g/m2.
  10. The paper fabric of any preceding claim, characterized in that
    the paper fabric has power consumption in a range from 50 W/m2 to 5000 W/m2, preferably power consumption in a range from 100 W/m2 to 3700 W/m2, particularly preferably power consumption in a range from 100 W/m2 to 1000 W/m2, further particularly preferably power consumption in a range from 250 W/m2 to 750 W/m2.
  11. The paper fabric of any preceding claim, characterized in that
    the paper fabric has a surface temperature in a range from 15°C to 130°C, preferably a surface temperature in a range from 35°C to 100°C, particularly preferably a surface temperature in a range from 15°C to 99°C, further particularly preferably a surface temperature in a range from 75°C to 130°C.
  12. A method of producing a paper fabric according to any preceding claim, comprising the steps of:
    - providing a material suspension of cellulose-containing fiber material and water;
    - adding at least one chemical additive;
    - adding the carbon fibers, the content of carbon fibers being more than 35% or between more than 35% and 99%, preferably between 45% and 85%, particularly preferably between 50% and 80%, further particularly preferably more than 50%;
    - dewatering the material suspension and producing the electrically conductive paper fabric;
    - mechanically dewatering and drying the electrically conductive paper fabric.
  13. The method of claim 12, characterized in that at least part of the carbon fibers are recycled carbon fibers for which, for example, pyrolytic processing of the carbon fiber composite materials is employed including deresination by sublimation.
  14. The method of any of claims 12 to 13, characterized in that the fiber-length distribution of the recycled carbon fibers is accomplished using a size-reduction stage.
  15. Use of the electrically conductive paper fabric of any of claims 1 to 11 as heating paper, particularly as a heating element in floors, walls, wallpapers, containers, fabrics, clothing, table tops, heating plates, heating mats, automotive interior heaters, particularly door heaters, seat heaters, dashboard heaters, for radiation protection, combinations thereof and the like.
EP14156382.5A 2013-02-26 2014-02-24 Electrically conductive paper structure Active EP2770104B1 (en)

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WO2020224800A1 (en) 2019-05-09 2020-11-12 Giesecke+Devrient Currency Technology Gmbh Electrically conductive paper structure, method for manufacturing same and use
EP3892794A1 (en) 2020-04-08 2021-10-13 Flooring Technologies Ltd. Covering system for a floor, a wall and/or a ceiling
EP3978233A1 (en) 2020-10-05 2022-04-06 Giesecke+Devrient Currency Technology GmbH Heatable composite material for use in the manufacture of modernisation, renovation or retrofitting of buildings, parts of buildings or the like
DE102022112515A1 (en) 2022-05-18 2023-11-23 Saint-Gobain Rigips Gmbh METHOD FOR PRODUCING A PLATE-SHAPED SURFACE HEATING ELEMENT AND SURFACE HEATING ELEMENT PRODUCED BY THIS METHOD, AND WALL SECTION OR CEILING SECTION OR FLOOR SECTION HAVING THE SURFACE HEATING ELEMENT
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DE102013109772A1 (en) * 2013-09-06 2015-03-12 RESO GmbH & Co. KG Paper structure and its production by wet process of carbon fibers
CN106182340A (en) * 2015-05-05 2016-12-07 合肥四达环境系统工程科技有限公司 Radiation protection board
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WO2020224800A1 (en) 2019-05-09 2020-11-12 Giesecke+Devrient Currency Technology Gmbh Electrically conductive paper structure, method for manufacturing same and use
EP3892794A1 (en) 2020-04-08 2021-10-13 Flooring Technologies Ltd. Covering system for a floor, a wall and/or a ceiling
WO2021204963A1 (en) 2020-04-08 2021-10-14 Flooring Technologies Ltd. Covering system for a floor, a wall and/or a ceiling
EP3978233A1 (en) 2020-10-05 2022-04-06 Giesecke+Devrient Currency Technology GmbH Heatable composite material for use in the manufacture of modernisation, renovation or retrofitting of buildings, parts of buildings or the like
DE102020006085A1 (en) 2020-10-05 2022-04-07 Giesecke+Devrient Currency Technology Gmbh Heatable composite material for use in the manufacture, modernization, refurbishment or renovation of buildings, parts of buildings or the like
DE102022112515A1 (en) 2022-05-18 2023-11-23 Saint-Gobain Rigips Gmbh METHOD FOR PRODUCING A PLATE-SHAPED SURFACE HEATING ELEMENT AND SURFACE HEATING ELEMENT PRODUCED BY THIS METHOD, AND WALL SECTION OR CEILING SECTION OR FLOOR SECTION HAVING THE SURFACE HEATING ELEMENT
DE102022130277A1 (en) 2022-11-16 2024-05-16 Giesecke+Devrient Currency Technology Gmbh Electrically conductive paper structure, method for producing the same and use
EP4372146A1 (en) 2022-11-16 2024-05-22 Giesecke+Devrient Currency Technology GmbH Electrically conductive paper structure, method for producing the same and use thereof

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