EP2127476B1 - Heating element, and heatable pane comprising a heating element - Google Patents
Heating element, and heatable pane comprising a heating element Download PDFInfo
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- EP2127476B1 EP2127476B1 EP08701394.2A EP08701394A EP2127476B1 EP 2127476 B1 EP2127476 B1 EP 2127476B1 EP 08701394 A EP08701394 A EP 08701394A EP 2127476 B1 EP2127476 B1 EP 2127476B1
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- heating element
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- carbon nanotubes
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Images
Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/84—Heating arrangements specially adapted for transparent or reflecting areas, e.g. for demisting or de-icing windows, mirrors or vehicle windshields
- H05B3/86—Heating arrangements specially adapted for transparent or reflecting areas, e.g. for demisting or de-icing windows, mirrors or vehicle windshields the heating conductors being embedded in the transparent or reflecting material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/013—Heaters using resistive films or coatings
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2214/00—Aspects relating to resistive heating, induction heating and heating using microwaves, covered by groups H05B3/00, H05B6/00
- H05B2214/04—Heating means manufactured by using nanotechnology
Definitions
- the invention relates to a heating element with an electrical conductor and a heated disc with such a heating element.
- heating element To generate heat in a heating element is usually passed through a current conductor. This is due to a voltage drop across an ohmic resistance to the conversion of electrical energy into heat energy.
- Such heating elements are used for a variety of uses. For the use of heating elements in heated disks, it is known to feed thin wires into the disk and to use these wires as a conductor for heating the disc. In addition to relatively high production costs are visual impairments and uneven heating of the disc to accept.
- pane both mineral glass panes and panes made of plastic glass are referred to as a pane.
- the use of such discs with a heating element is of particular interest in motor vehicles and aircraft.
- possible applications are heated visors of protective helmets, such as motorcycle helmets, or mirrors or displays of measuring instruments that are used for example in polar regions.
- a heating element which consists of several layers, including a disposed between the carrier layer and the adhesive layer electrically conductive layer.
- the WO 20061122736 A2 describes the production of a so-called special Bucky paper.
- a bucky paper is a nonwoven fabric made of nanotubes, which makes it nontransparent. The CNTs are absorbed by fibers.
- the object of the invention is to provide a heating element that allows uniform heating of a surface and at the same time resistant, easy to install and inexpensive.
- the heating element it has been recognized that it is advantageous to use a transparent sheet or band-shaped structure, hereinafter referred to as sheet-like structure, as the heating element.
- the fabric is constructed of at least three layers, each with different functionalities, namely a carrier layer, a current-conducting layer and an adhesive layer. These layers are all transparent so that the heating element as such is also transparent and can also be used in conjunction with panes.
- the carrier layer serves as a carrier of the other two layers. This should be tuned so that the structure as a whole is sufficiently flexible and well applicable.
- the current-conducting layer serves to fulfill the actual heating function. It should therefore allow a sufficiently high current flow. Furthermore, a current flow through the other layers should be largely avoided.
- the adhesive layer in turn serves for application of the fabric to any desired substrates. Depending on the substrate and field of application, special requirements, such as high bond strength, temperature and weather resistance and the like, are to be met.
- the layer structure has a further advantage in that the current-conducting layer is arranged between the carrier layer and the adhesive layer. This arrangement has the advantage that the current-conducting layer is protected against negative external influences, such as scratching and weathering.
- Transparency in the sense of the invention is understood as meaning a light transmission of at least 50% of the irradiated intensity.
- This transmittance can be e.g. according to DIN 5036 Part 3 or ASTM D 1003-00.
- a light transmission of at least 70% is achieved.
- the electrically conductive layer is formed such that it allows a substantially uniform heating over the sheet. Accordingly, the temperature difference in the plane of the fabric should not be greater than 20% of the maximum temperature reached in the plane of the fabric, apart from edge regions, for example in the area of the contacting.
- the heating power may be increased at other than the intended speed in the corresponding areas.
- the electrically conductive layer fulfills the heating function in that with the heating element a heating rate in air, starting from room temperature of at least 1 ° C / min., More preferably of at least 3 ° C / min. is reached.
- the heating power should be sufficient under the conditions mentioned at least for a temperature increase of 3 ° C, preferably for a temperature increase of at least 5 ° C.
- the current-conducting layer is formed so that at least 90%, preferably 95%, more preferably 98% of the total current flowing through the heating element flows through it.
- This can be realized for example by a corresponding thickness of and / or a correspondingly selected concentration of carbon nanotubes in the current-conducting layer.
- the current-carrying layer contains carbon nanotubes (CNT). These materials are conductive to an enormous extent and can also easily build a conductive network through their fibrous structure, so that hereby sufficient for the generation of heat conductivity is achieved even at a very low level in the current-conducting layer. This allows a particularly simple way to achieve the desired transparency of the current-conducting layer.
- the carbon nanotubes should be used as a filler in an amount of at least 0.01% by weight.
- heating element it may be desirable for certain areas of application of the heating element, if this has areas with different heating power, that is, for example, in the edge region, a higher heating power is achieved, as in the middle of the heating element or vice versa.
- Such different heating powers within the heating element can be easily achieved e.g. realize by a partially different thickness of the electrically conductive layer, in which a higher heat output is to be achieved, and / or by a partially different concentration of carbon nanotubes within the electrically conductive layer.
- the electrically conductive layer consists essentially of carbon nanotubes even without further additives, such as e.g. Binder exists.
- the anchoring of the layer on the carrier material is then effected essentially by van der Waals forces and supported by the overlying adhesive layer.
- a further advantageous embodiment according to claim 4 is that the carbon nanotubes are embedded in a transparent matrix.
- the carbon nanotubes can thus be permanently fixed in the layer and shielded from external influences, whereby an increased long-term stability can be achieved.
- with high transparency of the matrix increases the overall transparency of the heating element,
- a polymeric binder is used as the matrix material, which consists of a solution or dispersion in one or more organic solvents or Water is transferred to the current-conducting layer.
- This can be done, for example, by coating the solution or dispersion on the support material and then evaporating off the solvent or dispersant. It is advantageous here that it is easier to produce very thin and thus very transparent layers from the solution or dispersion than is possible from 100% systems, that is to say systems which contain no solvent and no dispersant, for example radiation-curing lacquers.
- the monomers used to prepare the matrix material are chosen in particular such that the resulting polymers can be used as PSAs at room temperature or higher temperatures, preferably such that the resulting polymers have pressure-sensitive adhesive properties according to the Handbook of Pressure Sensitive Adhesive Technology Donatas Satas (van Nostrand, New York 1989).
- the glass transition temperature which is frequently below the room temperature for these materials, and the low crosslinking density with correspondingly low modulus of elasticity give the carbon nanotubes greater mobility, which leads to an increase in network formation. This can reduce the amount of carbon nanotube used, which increases transparency and lowers costs.
- the monomers are very preferably selected in accordance with the above and the quantitative composition of the monomer mixture is advantageously selected such that the Fox equation (G1) (see TG Fox, Bull. Am. Phys Soc., 1 (1956) 123) gives the desired T G value for the polymer.
- G1 Fox equation (G1) (see TG Fox, Bull. Am. Phys Soc., 1 (1956) 123) gives the desired T G value for the polymer.
- 1 T G ⁇ n w n T G . n
- n the number of runs via the monomers used
- W n the mass fraction of the respective monomer unit n (wt .-%) and T G, n the respective glass transition temperature of the homopolymer obtained from the respective monomers n in K.
- Acrylate PSAs are particularly suitable as adhesive components which are obtainable, for example, by free-radical polymerization and which are based at least in part on at least one acrylic monomer of the general formula (1), wherein R 1 is H or a CH 3 radical and R 2 is H or is selected from the group of saturated, unbranched or branched, substituted or non-substituted C 1 to C 30 alkyl radicals is selected.
- the at least one acrylic monomer should have a mass fraction of at least 50% in the PSA.
- the advantage of acrylic PSAs is their high transparency and their good thermal and aging resistance.
- At least two surface areas are provided in the heating element, can be passed through the current in the electrically conductive layer. These surface areas are provided in the plane of the adhesive layer, wherein in these areas no adhesive layer or another type of electrically conductive layer, that is a different than the current-conducting layer, is arranged.
- This different type does not necessarily have to be transparent, since it is provided only for electrical contacting of the conductive layer and is therefore preferably arranged only in the edge regions of the heating element.
- the electrical conductivity of this layer is at least 10 times higher than the electrical conductivity of the current-conducting layer. This has the advantage that the layer which essentially conducts the current can be connected more easily to a current source lying outside the heating element than would be possible via the end faces of the heating element.
- connection to the current source is alternatively achieved in a further advantageous embodiment by two further transparent layers which are arranged above and below the current-conducting layer and which are likewise electrically conductive, these layers having an electrical conductivity which is at least 10 times higher than the current-conducting layer ,
- These layers may consist, for example, of vapor-deposited, sputtered-on or particulate metallic or metal oxide layers, such as, for example, indium tin oxide (ITO), or else intrinsically conductive polymers, for example those available under the trade name Baytron from HCStarck (Leverkusen).
- ITO indium tin oxide
- An appropriate structure is in Fig. 2 shown.
- Carbon nanotubes are microscopic tubular structures (molecular nanotubes) made of carbon. Their walls, like the fullerenes or, like the planes of the graphite, consist only of carbon, the carbon atoms occupying a honeycomb-like structure with hexagons and three binding partners each (dictated by sp 2 hybridization).
- the diameter of the tubes is in the range of 0.4 nm to 100 nm. Lengths of 0.5 ⁇ m to several millimeters for individual tubes and up to 20 cm for tube bundles are achieved.
- the electrical conductivity within the tube is metallic or semiconducting.
- Carbon tubes are also known which are superconducting at low temperatures.
- the carbon nanotubes can also be composed of two to about 30 graphitic layers, with two layers also often being referred to as double-walled carbon nanotubes (DWNTs).
- the walls of the single-walled carbon nanotubes (SWNTs) as well as the multi-walled carbon nanotubes (MWNTs) may have a "normal", an armchair, a zigzag, or a chiral structure that differ in degree of twist ,
- the diameter of the CNT can be between less than one and 100 nm and the tubes can be up to one millimeter long (" Polymers and carbon nanotubes - dimensionality, interactions and nanotechnology ", I. Szleifer, R. Yerushalmi-Rozen, Polymer 46 (2005), 7803 ).
- the heating element according to the invention it is advantageous for the heating element according to the invention to use carbon nanotubes with an average length of more than 10 microns, since with increasing length less carbon nanotubes are needed for sufficient conductivity and thus increases the transparency of the heating element.
- carbon nanotubes with an average outside diameter of less than 40 nm is advantageous for the heating element according to the invention.
- the mobility increases with decreasing outside diameter, whereby a network can be formed more easily and thus less carbon nanotubes can be formed Conductivity needed.
- the transparency of the heating element can be increased.
- the outside diameter decreases, the light scattering by the carbon nanotubes themselves decreases, thereby increasing the transparency as well.
- the carbon nanotubes have an average ratio of length to outer diameter of at least 250, since in this case a particularly high transparency with sufficient electrical conductivity can be achieved by combining the above-mentioned advantages in terms of length and diameter.
- the chemical modification simplifies mixing and / or dispersing with the polymer matrix, as it facilitates the singulation of the carbon nanotubes.
- the chemically modified CNT also interact sterically with the polymer matrix, and in other embodiments, in turn, the chemical interaction involves covalent attachment of the CNT or CNT derivatives to the polymer matrix, resulting in crosslinking and, thus, advantageously high mechanical stability of the layer.
- Modified carbon nanotubes are available, for example, from the companies FutureCarbon, Bayreuth, and Zyvex, Richardson (Texas, USA), under the trade name NanoSolve®.
- a preferred embodiment of the heating element is characterized in that the carbon nanotubes show a single carbon layer in the front view, so it is single-walled carbon nanotubes, which are also referred to as single-walled carbon nanotubes.
- the single-walled carbon nanotubes scatter the light less than multi-walled carbon nanotubes, so that a comparatively greater transparency can be achieved.
- heating element is characterized in that the carbon nanotubes show several carbon layers in the end view, so find multi-walled carbon nanotubes use, which are also referred to as double or multi-walled carbon nanotubes. These are available at a lower cost than the single-walled carbon nanotubes.
- the carbon nanotubes are aligned within the electrically conductive layer in a preferred direction.
- This alignment is advantageously carried out in the direction of the current flow predetermined by the position of the contact electrodes.
- a network of carbon nanotubes stretched in the direction of current flow is achieved, which ensures sufficient electrical conductivity even at a lower concentration of carbon nanotubes than in an isotropic network.
- the reduced concentration improves transparency and reduces costs.
- the alignment can be achieved, for example, in the case of the coating of the essentially the current-conducting layer out of a liquid phase by rheological effects (shear or strain in the flow).
- the application of an electrical voltage or an external electromagnetic field to the still flowable layer after application can also be used.
- the orientation at crystallite boundaries possible, such as in partially crystalline polymers, which are preferably drawn below the crystallization temperature, or at phase boundaries of multiphase matrix systems, such as block copolymers with preferably cylindrical or lamellar morphology. It is also possible to align the carbon nanotubes with structures that are present in the carrier layer or the adhesive layer, as is known from the field of liquid crystal polyners (LCP).
- LCP liquid crystal polyners
- the carbon nanotubes are among the most conductive fillers of all, it may be advantageous to add further conductive components to the current-conducting layer, since this can reduce costs or increase the conductivity and / or transparency.
- Suitable additives are nanoscale metal oxides, in particular indium zinc oxide or otherwise doped zinc oxides.
- the addition of intrinsically conductive polymers is advantageous in this sense (“ Synthesis and Characterization of Conducting Polythiophene / Carbon Nanotubes Composites "MS Lee et al., J. Pol. Sci. A, 44 (2006) 5283 ).
- the heating element is characterized in that the adhesive layer is formed as a self-adhesive layer (pressure sensitive adhesive).
- Self-adhesive compositions are permanently tacky at room temperature and therefore have a sufficiently low viscosity and high tack, so that they wet the surface of the respective adhesive base even at low pressure. This dosage form can be handled more easily than hot melt adhesives or liquid adhesive systems, requires no heating or other energy input during application and is generally free from chemical reactions after application.
- acrylate-based adhesive refers to any adhesive which, in addition to other optional constituents, comprises a base adhesive whose adhesive properties are determined or at least to a considerable extent determined by a polymer whose backbone comprises acrylate-type monomers.
- acrylate PSAs are suitable as self-adhesive layers which are based at least partly on at least one acrylic-type monomer.
- the advantage of acrylic PSAs is their high transparency and their good thermal and aging resistance.
- the polymer of the base adhesive of the acrylate-based adhesive preferably has a content of acrylate-type monomers of 50% by weight or more.
- Suitable base polymers are, in particular, those acrylate-based polymers which are obtainable, for example, by free-radical polymerization.
- the heating element is characterized in that the self-adhesive is a Styrolblockcopolymermasse.
- the self-adhesive is a Styrolblockcopolymermasse.
- the self-adhesive may, of course, in addition to the base adhesive also other additives such as fillers, especially nanoscale fillers that do not scatter the light and thus obtain the transparency, rheological additives, additives to improve adhesion, plasticizers, resins, elastomers, anti-aging agents (antioxidants) , Light stabilizers, UV absorbers and other auxiliaries and additives, for example, flow and leveling agents and / or wetting agents such as surfactants or catalysts.
- the heating element is characterized in that the self-adhesive composition has a transparency greater than 70%, preferably greater than 80%, especially preferably greater than 90%. This can be realized, for example, with a layer thickness of 30 ⁇ m.
- the high transparency has the advantage that the entire heating element has an increased transparency.
- the latter measure achieves a very smooth surface of the self-adhesive layer, which scatters and reflects the light less.
- the roughness R z is accordingly less than 0.5 ⁇ m, preferably less than 0.3 ⁇ m in accordance with DIN EN ISO 4287.
- Heating elements according to the invention can be used in particular for heatable panes, be they made of mineral glass or of plastic glass such as Plexiglas, preferably for a motor vehicle, in particular also for exterior rearview mirrors, or for an aircraft. Further fields of use of such glass panes are helmet visors or spectacle glazings, e.g. for ski goggles. In such and many other fields of application, it is advantageous to limit the transparency of the heating element, since this can then simultaneously act as a glare protection.
- a further preferred embodiment of the heating element has a transparency of at most 80%. This can e.g. be achieved by coloring carrier material and / or adhesive layer. However, it is preferred to select the type of carbon nanotube used in the essentially the current-conducting layer so that the desired degree of transparency in this layer is established with sufficient heating function at the same time. This has the advantage that no further measures in carrier material and adhesive layer for adjusting the transparency must be taken.
- Fig. 1 shows a schematic view of an inventive designed as a sheet heating element.
- the sheet has a carrier layer 1, an electrically conductive layer 2 and an adhesive layer 3.
- the current-conducting layer 2 is arranged between carrier layer 1 and adhesive layer 3 so as to be largely protected against the effects of weathering.
- Fig. 1 to see an electrical contact 4 for the current-conducting layer 2.
- no adhesive layer 3 is provided in two area regions, which are arranged here and preferably at the edge of the heating element.
- the current-conducting layer 2 is covered there with a different type of electrically conductive layer with greater electrical conductivity 4.
- a current feed into the current-conducting layer 2 is possible.
- Fig. 2 shows a schematic view of another inventive designed as a sheet heating element.
- the sheet has a carrier layer 1, an electrically conductive layer 2 and an adhesive layer 3.
- the current-conducting layer 2 is arranged between carrier layer 1 and adhesive layer 3.
- Fig. 2 to see an electrical contact for the current-conducting layer 2.
- two further transparent layers 5 are arranged above and below the current-conducting layer 2, which are likewise electrically conductive, wherein these layers 5 have an electrical conductivity which is at least 10 times higher than the current-conducting layer 2.
- FIG. 3 is an inventive structure as in FIG. 2 represented, between the adhesive layer 3 associated higher electrically conductive layer 5 and the current-conducting layer 2, a further layer 6 is arranged, which stabilizes the higher electrically conductive layer 5 in order to avoid fractures in this layer 5 and thus to ensure a durable contact ,
- FIG. 4 shows a heated disc 7 according to the invention with a heating element, which, as in FIG. 1 is constructed described.
- An aqueous dispersion of carbon nanotubes was prepared.
- the method of Yerushalmi-Rozen et al. used R. Shvartzman-Cohen, Y. Levi-Kalisman, E. Nativ-Roth, R. Yerushalmi-Rozen, Langmuir 20 (2004), 6085-6088 ), in the Triblock copolymers (PEO-b-PPO-b-PEO) can be used as stabilizers.
- the middle block has a higher affinity for the CNTs than the endblocks, which due to the large hydrodynamic radius lead to steric interactions between the carbon nanotubes.
- the hydrodynamic radius of the stabilizers is greater than the range at which the van der Waais forces are still effective.
- ATI-MWNT-001 Muli-walled CNT, unbound as grown, 95%, 3 to 5 layers, average diameter 35 nm, average length 100 microns, Fa. Ahwahnee, San Jose, USA
- the stabilizer was dissolved in a concentration of 1% by weight in demineralized water.
- a 1 wt% dispersion of carbon nanotubes was then prepared in this solution using an ultrasonic bath as a dispersing aid. After four hours of ultrasound treatment, approximately 70% of the CNTs were dispersed (optical estimation) and the dispersion was stable for several days until further processing. The undispersed nanotubes were filtered off.
- the dispersion was knife-coated onto a 23 ⁇ m thick PET film and dried to give a dry layer thickness of about 0.1 ⁇ m.
- the heating element showed at a voltage of 12.8 V applied a heating rate of about 10 ° C / min and reached, starting from room temperature, an equilibrium temperature of 39 ° C, which was measured on the adhesive.
- the heating element showed at a voltage of 12.8 V applied a heating rate of about 6 ° C / min and reached, starting from room temperature, an equilibrium temperature of 28 ° C, which was measured on the adhesive.
- the dispersion was knife-coated onto a 23 ⁇ m thick PET film and dried to give a dry layer thickness of about 2 ⁇ m.
- This layer was crosslinked by means of UV radiation with a UV-C dose of 36 mJ / cm 2 by means of a medium-pressure mercury radiator.
- the heating element showed at a voltage of 12.8 V applied a heating rate of about 15 ° C / min and reached from room temperature ⁇ an equilibrium temperature of 45 ° C, which was measured on the adhesive.
Landscapes
- Surface Heating Bodies (AREA)
- Laminated Bodies (AREA)
- Resistance Heating (AREA)
Description
Die Erfindung betrifft ein Heizelement mit einem elektrischen Stromleiter sowie eine beheizbare Scheibe mit einem derartigen Heizelement.The invention relates to a heating element with an electrical conductor and a heated disc with such a heating element.
Zur Wärmeerzeugung wird in einem Heizelement üblicherweise Strom durch einen Stromleiter geleitet. Dabei kommt es durch einen Spannungsabfall an einem ohmschen Widerstand zur Umwandlung elektrischer Energie in Wärmeenergie. Derartige Heizelemente werden für vielfältige Verwendungen eingesetzt. Für den Einsatz von Heizelementen bei beheizbaren Scheiben ist es bekannt, dünne Drähte in die Scheibe einzuziehen und diese Drähte als Stromleiter zum Aufheizen der Scheibe zu verwenden. Neben relativ hohen Herstellungskosten sind dabei Sichtbehinderungen sowie eine ungleichmäßige Erwärmung der Scheibe hinzunehmen.To generate heat in a heating element is usually passed through a current conductor. This is due to a voltage drop across an ohmic resistance to the conversion of electrical energy into heat energy. Such heating elements are used for a variety of uses. For the use of heating elements in heated disks, it is known to feed thin wires into the disk and to use these wires as a conductor for heating the disc. In addition to relatively high production costs are visual impairments and uneven heating of the disc to accept.
Als Scheibe werden dabei sowohl Mineralglasscheiben als auch Scheiben aus Kunststoffgläsern bezeichnet. Die Verwendung derartiger Scheiben mit einem Heizelement ist insbesondere bei Kraft- und Luftfahrzeugen von Interesse. Ferner sind mögliche Anwendungsgebiete beheizbare Visiere von Schutzhelmen, wie Motorradhelme, oder Spiegel oder Displays von Messgeräten, die beispielsweise in Polarregionen eingesetzt werden.In this case, both mineral glass panes and panes made of plastic glass are referred to as a pane. The use of such discs with a heating element is of particular interest in motor vehicles and aircraft. Furthermore, possible applications are heated visors of protective helmets, such as motorcycle helmets, or mirrors or displays of measuring instruments that are used for example in polar regions.
Es ist ferner bekannt, so genannte elektrisch leitfähige Folien als Heizelement zu verwenden. Deren Einsatzgebiet ist aufgrund eines begrenzten Stromdurchflusses und einer nicht ausreichenden Transparenz allerdings begrenzt. Bei erhöhtem Stromdurchfluss treten bei diesen leitfähigen Folien oftmals Schäden in den Folien auf, die die Funktionalität beeinträchtigen. Zudem weisen die bei derartigen Folien verwendeten intrinsisch leitfähigen Polymere nur eine geringe Dauerstabilität auf.It is also known to use so-called electrically conductive films as a heating element. However, their field of application is limited due to a limited current flow and an insufficient transparency. With increased current flow occur in these conductive films often damage in the films, which affect the functionality. In addition, the intrinsically conductive polymers used in such films have only a low durability.
Aus der
Die
Aufgabe der Erfindung ist es, ein Heizelement anzugeben, das eine gleichmäßige Erwärmung einer Fläche ermöglicht und gleichzeitig beständig, leicht montierbar und preiswert ist.The object of the invention is to provide a heating element that allows uniform heating of a surface and at the same time resistant, easy to install and inexpensive.
Die vorliegende Erfindung wird bei einem Heizelement mit den Merkmalen des Oberbegriffs von Anspruch 1 durch die Merkmale des kennzeichnenden Teils von Anspruch 1 gelöst. Bevorzugte Ausgestaltungen und Weiterbildungen sind Gegenstand der Unteransprüche.The present invention is achieved in a heating element having the features of the preamble of
Erfindungsgemäß ist erkannt worden, dass es vorteilhaft ist, ein transparentes Flächengebilde oder bandförmiges Gebildes, im Folgenden nur Flächengebilde genannt, als Heizelement zu verwenden. Das Flächengebilde ist dabei aus mindestens drei Schichten mit jeweils unterschiedlichen Funktionalitäten aufgebaut, nämlich einer Trägerschicht, einer stromleitenden Schicht und einer Klebeschicht. Diese Schichten sind alle transparent, so dass das Heizelement als solches ebenfalls transparent ist und auch in Verbindung mit Scheiben verwendet werden kann.According to the invention, it has been recognized that it is advantageous to use a transparent sheet or band-shaped structure, hereinafter referred to as sheet-like structure, as the heating element. The fabric is constructed of at least three layers, each with different functionalities, namely a carrier layer, a current-conducting layer and an adhesive layer. These layers are all transparent so that the heating element as such is also transparent and can also be used in conjunction with panes.
Durch die Verwendung der mehreren Schichten mit unterschiedlichen Aufgaben, wird eine Entkoppelung der Funktionalitäten erzielt, durch die es möglich ist, jede Schicht auf die jeweiligen Anforderungen individuell abzustimmen. Dadurch können Anforderungen bezüglich des Heizelements für unterschiedlichste Verwendungen einfacher und kostengünstiger realisiert werden. Die Trägerschicht dient als Träger der beiden anderen Schichten. Dieser sollte so abgestimmt sein, dass das Gebilde als ganzes hinreichend flexibel und gut anwendbar ist. Die stromleitende Schicht dient zur Erfüllung der eigentlichen Heizfunktion. Sie sollte demzufolge einen ausreichend hohen Stromfluss ermöglichen. Ferner sollte ein Stromfluss durch die anderen Schichten weitgehend vermieden werden. Die Klebeschicht wiederum dient zur Applikation des Flächengebildes auf beliebigen Untergründen. Je nach Untergrund und Anwendungsgebiet sind insofern besondere Anforderungen, wie hohe Klebkraft, Temperatur- und Witterungsbeständigkeit und dergleichen, zu erfüllen. Der Schichtaufbau hat einen weiteren Vorteil darin, dass die stromleitende Schicht zwischen der Trägerschicht und der Klebeschicht angeordnet ist. Diese Anordnung hat den Vorteil, dass die stromleitende Schicht gegen negative äußere Einflüsse, wie z.B. Verkratzen und gegen Witterungseinflüsse, geschützt ist.By using the multiple layers with different tasks, a decoupling of the functionalities is achieved, by which it is possible to tailor each layer individually to the respective requirements. As a result, requirements for the heating element for a wide variety of uses can be realized in a simpler and more cost-effective manner. The carrier layer serves as a carrier of the other two layers. This should be tuned so that the structure as a whole is sufficiently flexible and well applicable. The current-conducting layer serves to fulfill the actual heating function. It should therefore allow a sufficiently high current flow. Furthermore, a current flow through the other layers should be largely avoided. The adhesive layer in turn serves for application of the fabric to any desired substrates. Depending on the substrate and field of application, special requirements, such as high bond strength, temperature and weather resistance and the like, are to be met. The layer structure has a further advantage in that the current-conducting layer is arranged between the carrier layer and the adhesive layer. This arrangement has the advantage that the current-conducting layer is protected against negative external influences, such as scratching and weathering.
Unter Transparenz im Sinne der Erfindung wird eine Lichttransmission von mindestens 50% der eingestrahlten Intensität verstanden. Dieser Transmissionsgrad kann z.B. nach DIN 5036 Teil 3 oder ASTM D 1003-00 ermittelt werden. In bevorzugter Ausgestaltung wird eine Lichttransmission von mindestens 70% erzielt.Transparency in the sense of the invention is understood as meaning a light transmission of at least 50% of the irradiated intensity. This transmittance can be e.g. according to DIN 5036
In bevorzugter Ausgestaltung ist die stromleitende Schicht derart ausgebildet, dass sie eine im Wesentlichen gleichmäßige Erwärmung über das Flächengebilde ermöglicht. Die Temperaturdifferenz in der Ebene des Flächengebildes sollte demgemäß, abgesehen von Randbereichen beispielsweise im Bereich der Kontaktierung, nicht größer als 20 % des maximal in der Ebene des Flächengebildes erreichten Temperaturendwerts sein.In a preferred embodiment, the electrically conductive layer is formed such that it allows a substantially uniform heating over the sheet. Accordingly, the temperature difference in the plane of the fabric should not be greater than 20% of the maximum temperature reached in the plane of the fabric, apart from edge regions, for example in the area of the contacting.
Alternativ kann aber auch vorgesehen werden, gezielt Bereiche auszubilden, in denen die Heizleistung erhöht ist, also einen Temperaturgradienten bezüglich der Heizleistung durch den Aufbau des Heizelements vorzugeben. Dies kann beispielsweise durch eine bereichsweise erhöhte Schichtdicke der stromleitenden Schicht erfolgen. Durch eine solche Ausgestaltung können üblicherweise auftretende Temperaturgradienten in einer Scheibe, z.B. durch bereichsweise schnelleres Abkühlen aufgrund von Luftverwirbelungen, ausgeglichen werden. Da solche Effekte jedoch geschwindigkeitsabhängig sind, ist dabei hinzunehmen, dass die Heizleistung bei anderen als der vorgesehenen Geschwindigkeit in den entsprechenden Bereichen gegebenenfalls erhöht ist.Alternatively, however, it may also be provided to specifically form regions in which the heating power is increased, that is to say to predetermine a temperature gradient with respect to the heating power due to the structure of the heating element. This can be done for example by a partially increased layer thickness of the current-conducting layer. By such a design, commonly occurring temperature gradients in a disk, e.g. be compensated by partially faster cooling due to air turbulence. However, since such effects are speed-dependent, it is to be assumed that the heating power may be increased at other than the intended speed in the corresponding areas.
Vorzugsweise erfüllt die stromleitende Schicht die Heizfunktion dahingehend, dass mit dem Heizelement eine Aufheizrate in Luft ausgehend von Raumtemperatur von mindestens 1 °C/min., weiter vorzugsweise von mindestens 3 °C/min. erreicht wird. Die Heizleistung sollte unter den genannten Bedingungen mindestens für eine Temperaturerhöhung von 3 °C, vorzugsweise für eine Temperaturerhöhung von mindestens 5 °C ausreichen.Preferably, the electrically conductive layer fulfills the heating function in that with the heating element a heating rate in air, starting from room temperature of at least 1 ° C / min., More preferably of at least 3 ° C / min. is reached. The heating power should be sufficient under the conditions mentioned at least for a temperature increase of 3 ° C, preferably for a temperature increase of at least 5 ° C.
Gemäß Anspruch 2 ist die stromleitende Schicht so ausgebildet, dass mindestens 90%, vorzugsweise 95%, weiter vorzugsweise 98% des insgesamt durch das Heizelement fließenden Stromes durch sie fließt. Dies kann beispielsweise durch eine entsprechende Dicke der und/oder eine entsprechend gewählte Konzentration von Carbon-Nanotubes in der stromleitenden Schicht realisiert sein. Eine solch bevorzugte Weiterbildung hat den Vorteil, dass Unfallgefahren durch die untergeordnete Leitfähigkeit der anderen Schichten vermieden sind.According to
Die stromleitende Schicht enthält Carbon-Nanotubes (CNT). Diese Materialien sind in enormen Maße leitfähig und können darüber hinaus durch ihre faserige Struktur leicht ein leitfähiges Netzwerk aufbauen, so dass hiermit eine für die Wärmeerzeugung ausreichende Leitfähigkeit bereits bei einem sehr geringen Anteil in der stromleitenden Schicht erreicht wird. Dies ermöglicht auf besonders einfache Weise, die gewünschte Transparenz der stromleitenden Schicht zu erzielen. Um eine ausreichende Leitfähigkeit zu erzielen sollte die Carbon-Nanotubes als Füllstoff in einer Menge von mindestens 0,01 Gew.-% verwendet werden.The current-carrying layer contains carbon nanotubes (CNT). These materials are conductive to an enormous extent and can also easily build a conductive network through their fibrous structure, so that hereby sufficient for the generation of heat conductivity is achieved even at a very low level in the current-conducting layer. This allows a particularly simple way to achieve the desired transparency of the current-conducting layer. In order to obtain sufficient conductivity, the carbon nanotubes should be used as a filler in an amount of at least 0.01% by weight.
Ferner kann es für bestimmte Anwendungsgebiete des Heizelementes wünschenswert sein, wenn dieses Bereiche mit unterschiedlicher Heizleistung aufweist, das heißt beispielsweise im Randbereich eine höhere Heizleistung erzielt wird, als in der Mitte des Heizelementes oder umgekehrt. Solch unterschiedliche Heizleistungen innerhalb des Heizelementes lassen sich auf einfache Weise z.B. realisieren durch eine bereichsweise unterschiedliche Dicke der stromleitenden Schicht, in denen eine höhere Heizleistung erzielt werden soll, und/oder durch eine bereichsweise unterschiedliche Konzentration an Carbon-Nanotubes innerhalb der stromleitenden Schicht.Furthermore, it may be desirable for certain areas of application of the heating element, if this has areas with different heating power, that is, for example, in the edge region, a higher heating power is achieved, as in the middle of the heating element or vice versa. Such different heating powers within the heating element can be easily achieved e.g. realize by a partially different thickness of the electrically conductive layer, in which a higher heat output is to be achieved, and / or by a partially different concentration of carbon nanotubes within the electrically conductive layer.
In einer weiter bevorzugten Ausgestaltung ist vorgesehen, dass die stromleitende Schicht im Wesentlichen aus Carbon-Nanotubes selbst ohne weitere Zusätze wie z.B. Bindemittel besteht. Die Verankerung der Schicht auf dem Trägermaterial wird dann im Wesentlichen durch Van-der-Waals-Kräfte bewirkt und durch die darüberliegende Klebeschicht unterstützt.In a further preferred embodiment, it is provided that the electrically conductive layer consists essentially of carbon nanotubes even without further additives, such as e.g. Binder exists. The anchoring of the layer on the carrier material is then effected essentially by van der Waals forces and supported by the overlying adhesive layer.
Eine weitere vorteilhafte Ausgestaltung gemäß Anspruch 4 besteht darin, dass die Carbon-Nanotubes in eine transparente Matrix eingebettet sind. Die Carbon-Nanotubes können so dauerhaft in der Schicht fixiert und von externen Einflüssen abgeschirmt werden, wodurch eine erhöhte Langzeitstabilität erzielt werden kann. Zudem steigt mit hoher Transparenz der Matrix die Gesamttransparenz des Heizelements,A further advantageous embodiment according to
Bevorzugt wird als Matrixmaterial ein polymeres Bindemittel eingesetzt, welches aus einer Lösung oder Dispersion in einem oder mehreren organischen Lösemitteln oder Wasser in die stromleitende Schicht überführt wird. Dies kann beispielsweise durch Beschichten der Lösung oder Dispersion auf das Trägermaterial und anschließendes Abdampfen des Löse- bzw. Dispergiermittels erfolgen. Vorteilhaft ist hier, dass aus der Lösung oder Dispersion leichter sehr dünne und damit sehr transparente Schichten hergestellt werden können, als dies aus 100%-Systemen möglich ist, also Systemen die kein Lösemittel und kein Dispergiermittel enthalten, wie z.B. strahlenhärtende Lacke. Zudem stehen marktseitig bereits Carbon-Nanotube-Dispersionen in organischen Lösemitteln und Wasser zur Verfügung (z.B. von den Firmen Eikos, Boston, unter dem Handelsnamen Invisicon™; Zyvex, Richardson (Texas, USA), unter dem Handelsnamen NanoSolve® und FutureCarbon GmbH, Bayreuth), die leicht in solche Bindemittelsysteme dispergiert werden können.Preferably, a polymeric binder is used as the matrix material, which consists of a solution or dispersion in one or more organic solvents or Water is transferred to the current-conducting layer. This can be done, for example, by coating the solution or dispersion on the support material and then evaporating off the solvent or dispersant. It is advantageous here that it is easier to produce very thin and thus very transparent layers from the solution or dispersion than is possible from 100% systems, that is to say systems which contain no solvent and no dispersant, for example radiation-curing lacquers. In addition, carbon nanotube dispersions in organic solvents and water are already available on the market (eg from the companies Eikos, Boston, under the trade name Invisicon ™ , Zyvex, Richardson (Texas, USA), under the trade names NanoSolve® and FutureCarbon GmbH, Bayreuth ) which can be easily dispersed in such binder systems.
Gemäß Anspruch 6 werden die zur Herstellung des Matrixmaterials dienenden Monomere insbesondere dermaßen gewählt, dass die resultierenden Polymere bei Raumtemperatur oder höheren Temperaturen als Haftklebemassen eingesetzt werden können, vorzugsweise derart, dass die resultierenden Polymere haftklebende Eigenschaften entsprechend dem "Handbook of Pressure Sensitive Adhesive Technology" von Donatas Satas (van Nostrand, New York 1989) besitzen. Durch die bei diesen Materialien häufig unterhalb der Raumtemperatur liegende Glasübergangstemperatur und die geringe Vernetzungsdichte mit dementsprechend niedrigem Elastizitätsmodul erlangen die Carbon-Nanotubes eine höhere Beweglichkeit, was zur Verstärkung der Netzwerkbildung führt. Dadurch kann die Einsatzmenge der Carbon-Nanotubes verringert werden, was die Transparenz erhöht und die Kosten senkt.According to
Zur Erzielung einer für Haftklebemassen bevorzugten Glasübergangstemperatur TG der Polymere von TG ≤ 25 °C, welche mittels der Differential Scanning Calorimetry ermittelt wird, werden entsprechend dem vorstehend Gesagten die Monomere sehr bevorzugt derart ausgesucht und die mengenmäßige Zusammensetzung der Monomermischung vorteilhaft derart gewählt, dass sich nach der Fox-Gleichung (G1) (vgl. T.G. Fox, Bull. Am. Phys. Soc. 1 (1956) 123) der gewünschte TG-Wert für das Polymer ergibt.
Hierin repräsentiert n die Laufzahl über die eingesetzten Monomere, Wn den Massenanteil der jeweiligen Monomereinheit n (Gew.-%) und TG,n die jeweilige Glasübergangstemperatur des Homopolymers erhalten aus den jeweiligen Monomeren n in K.Here n represents the number of runs via the monomers used, W n the mass fraction of the respective monomer unit n (wt .-%) and T G, n the respective glass transition temperature of the homopolymer obtained from the respective monomers n in K.
Es sind insbesondere Acrylathaftklebemassen als Klebstoffkomponente geeignet, welche etwa durch radikalische Polymerisation erhältlich sind und die zumindest teilweise auf mindestens einem Acrylmonomer der allgemeinen Formel (1) basieren,
In einer vorteilhaften Ausführung sind in dem Heizelement zumindest zwei Flächenbereiche vorgesehen, durch die Strom in die stromleitende Schicht geleitet werden kann. Diese Flächenbereiche sind in der Ebene der Klebeschicht vorgesehen, wobei in diesen Bereichen keine Klebeschicht oder eine andersartige elektrisch leitfähige Schicht, also eine andere als die stromleitende Schicht, angeordnet ist. Diese andersartige muss nicht zwingend transparent sein, da sie lediglich zur elektrischen Kontaktierung der leitenden Schicht vorgesehen ist und somit vorzugsweise nur in den Randbereichen des Heizelements angeordnet ist. Die elektrische Leitfähigkeit dieser Schicht ist mindestens 10flach höher als die elektrische Leitfähigkeit der stromleitenden Schicht. Dies hat den Vorteil, dass die im Wesentlichen den Strom leitende Schicht leichter mit einer außerhalb des Heizelements liegenden Stromquelle verbunden werden kann, als dies über die Stirnseiten des Heizelements möglich wäre.In an advantageous embodiment, at least two surface areas are provided in the heating element, can be passed through the current in the electrically conductive layer. These surface areas are provided in the plane of the adhesive layer, wherein in these areas no adhesive layer or another type of electrically conductive layer, that is a different than the current-conducting layer, is arranged. This different type does not necessarily have to be transparent, since it is provided only for electrical contacting of the conductive layer and is therefore preferably arranged only in the edge regions of the heating element. The electrical conductivity of this layer is at least 10 times higher than the electrical conductivity of the current-conducting layer. This has the advantage that the layer which essentially conducts the current can be connected more easily to a current source lying outside the heating element than would be possible via the end faces of the heating element.
Die Verbindung mit der Stromquelle wird alternativ in einer weiteren vorteilhaften Ausführung durch zwei weitere transparente Schichten, die oberhalb und unterhalb der stromleitenden Schicht angeordnet sind und die ebenfalls elektrisch leitfähig sind, erreicht, wobei diese Schichten eine gegenüber der stromleitenden Schicht mindestens 10fach höhere elektrische Leitfähigkeit aufweisen. Diese Schichten können beispielsweise aus aufgedampften, aufgesputterten oder partikulären metallischen oder metalloxidischen Schichten, wie z.B. Indium-Zinn-Oxid (ITO), oder auch intrinsisch leitfähigen Polymeren bestehen, wie sie z.B. unter dem Handelsnamen Baytron von H.C.Starck (Leverkusen) erhältlich sind. Ein entsprechender Aufbau ist in
Carbon-Nanotubes sind mikroskopisch kleine röhrenförmige Gebilde (molekulare Nanoröhren) aus Kohlenstoff. Ihre Wände bestehen wie die der Fullerene oder wie die Ebenen des Graphits nur aus Kohlenstoff, wobei die Kohlenstoffatome eine wabenartige Struktur mit Sechsecken und jeweils drei Bindungspartnern einnehmen (vorgegeben durch die sp2-Hybridisierung). Der Durchmesser der Röhren liegt im Bereich von 0.4 nm bis 100 nm. Längen von 0.5 µm bis zu mehreren Millimetern für einzelne Röhren und bis zu 20 cm für Röhrenbündel werden erreicht.Carbon nanotubes are microscopic tubular structures (molecular nanotubes) made of carbon. Their walls, like the fullerenes or, like the planes of the graphite, consist only of carbon, the carbon atoms occupying a honeycomb-like structure with hexagons and three binding partners each (dictated by sp 2 hybridization). The diameter of the tubes is in the range of 0.4 nm to 100 nm. Lengths of 0.5 μm to several millimeters for individual tubes and up to 20 cm for tube bundles are achieved.
Man unterscheidet zwischen ein- und mehrwandigen, zwischen offenen oder geschlossenen Röhren (mit einem Deckel, der einen Ausschnitt aus einer Fullerenstruktur hat) und zwischen leeren und gefüllten Röhren.A distinction is made between single and multi-walled, between open or closed tubes (with a lid that has a section of a fullerene structure) and between empty and filled tubes.
Je nach Detail der Struktur ist die elektrische Leitfähigkeit innerhalb der Röhre metallisch oder halbleitend. Es sind auch Kohlenstoffröhren bekannt, die bei tiefen Temperaturen supraleitend sind.Depending on the detail of the structure, the electrical conductivity within the tube is metallic or semiconducting. Carbon tubes are also known which are superconducting at low temperatures.
Aus der Zeitschrift "Science" ist ein Aufsatz mit dem Titel "
Die Carbon-Nanotubes können auch aus zwei bis etwa 30 graphitartigen Schichten aufgebaut sein, wobei bei zwei Schichten auch häufig von Double-walled Carbon-Nanotubes (DWNTs) gesprochen wird. Die Wände der Single-walled Carbon-Nanotubes (SWNTs) als auch der Multi-walled Carbon-Nanotubes (MWNTs) können eine "normale", eine Armchair-, eine Zickzack- oder eine chirale Struktur aufweisen, die sich im Grad der Verdrillung unterscheiden. Der Durchmesser der CNT kann zwischen weniger als einem und 100 nm liegen wobei die Röhren eine Länge bis zu einem Millimeter annehmen können ("
Vorteilhaft für das erfindungsgemäße Heizelement ist es, Carbon-Nanotubes mit einer durchschnittlicher Länge von mehr als 10 µm zu verwenden, da mit zunehmender Länge weniger Carbon-Nanotubes für eine ausreichende Leitfähigkeit gebraucht werden und somit die Transparenz des Heizelements steigt.It is advantageous for the heating element according to the invention to use carbon nanotubes with an average length of more than 10 microns, since with increasing length less carbon nanotubes are needed for sufficient conductivity and thus increases the transparency of the heating element.
Vorteilhaft für das erfindungsgemäße Heizelement ist zudem die Verwendung von Carbon-Nanotubes mit einem durchschnittlichen Außendurchmesser von weniger als 40 nm. Bei Carbon-Nanotubes steigt mit abnehmendem Außendurchmesser die Beweglichkeit, wodurch ein Netzwerk leichter gebildet werden kann und somit weniger Carbon-Nanotubes für eine ausreichende Leitfähigkeit gebraucht werden. Durch eine Reduktion der verwendeten Menge von Carbon-Nanotubes kann die Transparenz des Heizelements erhöht werden. Weiterhin sinkt mit abnehmendem Außendurchmesser die Lichtstreuung durch die Carbon-Nanotubes selbst, so dass auch hierdurch die Transparenz steigt.In addition, the use of carbon nanotubes with an average outside diameter of less than 40 nm is advantageous for the heating element according to the invention. With carbon nanotubes, the mobility increases with decreasing outside diameter, whereby a network can be formed more easily and thus less carbon nanotubes can be formed Conductivity needed. By reducing the amount of carbon nanotubes used, the transparency of the heating element can be increased. Furthermore, as the outside diameter decreases, the light scattering by the carbon nanotubes themselves decreases, thereby increasing the transparency as well.
Besonders bevorzugt ist es, wenn die Carbon-Nanotubes ein durchschnittliches Verhältnis von Länge zu Außendurchmesser von mindestens 250 aufweisen, da hierbei durch die Kombination der oben genannten Vorteile bezüglich Länge und Durchmesser eine besonders hohe Transparenz bei ausreichender elektrischer Leitfähigkeit erreicht werden kann.It is particularly preferred if the carbon nanotubes have an average ratio of length to outer diameter of at least 250, since in this case a particularly high transparency with sufficient electrical conductivity can be achieved by combining the above-mentioned advantages in terms of length and diameter.
In einigen Ausführungen ist es vorteilhaft die Oberfläche der Carbon Nanotubes chemisch zu funktionalisieren oder anderweitig zu modifizieren. Die chemische Modifikation vereinfacht das Mischen und/oder Dispergieren mit der Polymermatrix, da sie die Vereinzelung der Carbon-Nanotubes erleichtert. In einigen Ausführungen können die chemisch modifizierten CNT auch sterisch mit der Polymermatrix wechselwirken, und in anderen Ausführungen wiederum umfasst die chemische Wechselwirkung kovalente Anbindung der CNT oder CNT-Derivate an die Polymermatrix, was zu einer Vernetzung und damit zu einer vorteilhaft hohen mechanischen Stabilität der Schicht führt. Modifizierte Carbon Nanotubes sind beispielsweise von den Firmen FutureCarbon, Bayreuth, und Zyvex, Richardson (Texas, USA), unter dem Handelsnamen NanoSolve® erhältlich.In some embodiments, it is advantageous to chemically functionalize or otherwise modify the surface of the carbon nanotube. The chemical modification simplifies mixing and / or dispersing with the polymer matrix, as it facilitates the singulation of the carbon nanotubes. In some versions can the chemically modified CNT also interact sterically with the polymer matrix, and in other embodiments, in turn, the chemical interaction involves covalent attachment of the CNT or CNT derivatives to the polymer matrix, resulting in crosslinking and, thus, advantageously high mechanical stability of the layer. Modified carbon nanotubes are available, for example, from the companies FutureCarbon, Bayreuth, and Zyvex, Richardson (Texas, USA), under the trade name NanoSolve®.
Eine bevorzugte Ausführung des Heizelements ist dadurch gekennzeichnet, dass die Carbon-Nanotubes eine einzige Kohlenstoffschicht in der Stirnansicht zeigen, es sich also um einwandige Carbon-Nanotubes handelt, die auch als Single-walled Carbon-Nanotubes bezeichnet werden. Die einwandigen Carbon-Nanotubes streuen das Licht weniger als mehrwandige Carbon-Nanotubes, so dass eine vergleichsweise größere Transparenz erreichbar ist.A preferred embodiment of the heating element is characterized in that the carbon nanotubes show a single carbon layer in the front view, so it is single-walled carbon nanotubes, which are also referred to as single-walled carbon nanotubes. The single-walled carbon nanotubes scatter the light less than multi-walled carbon nanotubes, so that a comparatively greater transparency can be achieved.
Eine in anderer Weise bevorzugte Ausführung des Heizelements ist dadurch gekennzeichnet, dass die Carbon-Nanotubes mehrere Kohlenstoffschichten in der Stirnansicht zeigen, also mehrwandige Carbon-Nanotubes Verwendung finden, die auch als Double- oder Multi-walled Carbon-Nanotubes bezeichnet werden. Diese sind gegenüber den einwandigen Carbon-Nanotubes mit geringeren Kosten zu beziehen.An otherwise preferred embodiment of the heating element is characterized in that the carbon nanotubes show several carbon layers in the end view, so find multi-walled carbon nanotubes use, which are also referred to as double or multi-walled carbon nanotubes. These are available at a lower cost than the single-walled carbon nanotubes.
Vorteilhaft ist es auch, wenn die Carbon-Nanotubes innerhalb der stromleitenden Schicht in einer Vorzugsrichtung ausgerichtet sind. Diese Ausrichtung erfolgt vorteilhafterweise in der Richtung des von der Lage der Kontaktelektroden vorgegebenen Stromflusses. Durch die Ausrichtung wird ein in Stromflussrichtung gestrecktes Netzwerk von Carbon-Nanotubes erreicht, welches bereits bei geringerer Konzentration von Carbon-Nanotubes als in einem isotropen Netzwerk erforderlich eine ausreichende elektrische Leitfähigkeit gewährleistet. Mit der verringerten Konzentration verbessert sich die Transparenz und sinken die Kosten.It is also advantageous if the carbon nanotubes are aligned within the electrically conductive layer in a preferred direction. This alignment is advantageously carried out in the direction of the current flow predetermined by the position of the contact electrodes. As a result of the orientation, a network of carbon nanotubes stretched in the direction of current flow is achieved, which ensures sufficient electrical conductivity even at a lower concentration of carbon nanotubes than in an isotropic network. The reduced concentration improves transparency and reduces costs.
Die Ausrichtung kann z.B. bei der Beschichtung der im Wesentlichen den Strom leitenden Schicht aus einer flüssigen Phase heraus durch rheologische Effekte (Scherung oder Dehnung in der Strömung) erreicht werden. Auch das Anlegen einer elektrischen Spannung oder eines äußeren elektromagnetischen Feldes an die nach dem Aufbringen noch fließfähige Schicht kann genutzt werden. Weiterhin ist die Ausrichtung an Kristallitgrenzen möglich, wie z.B. bei teilkristallinen Polymeren, welche vorzugsweise unterhalb der Kristallisationstemperatur verstreckt werden, oder an Phasengrenzen mehrphasiger Matrixsysteme, wie z.B. Block-Copolymeren mit vorzugsweise zylindrischer oder lamellarer Morphologie. Möglich ist auch die Ausrichtung der Carbon-Nanotubes an Strukturen, die in der Trägerschicht oder der Klebeschicht vorhanden sind, wie dies aus dem Bereich der liquid crystal polyners (LCP) bekannt ist.The alignment can be achieved, for example, in the case of the coating of the essentially the current-conducting layer out of a liquid phase by rheological effects (shear or strain in the flow). The application of an electrical voltage or an external electromagnetic field to the still flowable layer after application can also be used. Furthermore, the orientation at crystallite boundaries possible, such as in partially crystalline polymers, which are preferably drawn below the crystallization temperature, or at phase boundaries of multiphase matrix systems, such as block copolymers with preferably cylindrical or lamellar morphology. It is also possible to align the carbon nanotubes with structures that are present in the carrier layer or the adhesive layer, as is known from the field of liquid crystal polyners (LCP).
Wenn auch die Carbon-Nanotubes zu den leitfähigsten Füllstoffen überhaupt zählen, so kann es doch vorteilhaft sein, der stromleitenden Schicht weitere leitfähige Komponenten hinzuzufügen, da hiermit Kosten gesenkt oder die Leitfähigkeit und/oder Transparenz erhöht werden kann. Geeignete Zusatzstoffe sind nanoskalige Metalloxide, insbesondere Indium-Zink-Oxid oder anderweitig dotierte Zinkoxide. Auch die Zugabe von intrinsisch leitfähigen Polymeren ist in diesem Sinne vorteilhaft ("
In einer weiteren vorteilhaften Ausführung ist das Heizelement dadurch gekennzeichnet, dass die Klebeschicht als Selbstklebeschicht (pressure sensitive adhesive) ausgebildet ist. Selbstklebemassen wirken bei Raumtemperatur permanent haftklebrig, weisen also eine hinreichend geringe Viskosität und eine hohe Anfassklebrigkeit auf, so dass sie die Oberfläche des jeweiligen Klebegrunds bereits bei geringem Andruck benetzen. Diese Darreichungsform kann gegenüber Heißschmelzklebern oder Flüssigklebersystemen leichter gehandhabt werden, erfordert bei der Applikation keine Erwärmung oder sonstige Energiezufuhr und ist in der Regel frei von chemischen Reaktionen nach der Applikation.In a further advantageous embodiment, the heating element is characterized in that the adhesive layer is formed as a self-adhesive layer (pressure sensitive adhesive). Self-adhesive compositions are permanently tacky at room temperature and therefore have a sufficiently low viscosity and high tack, so that they wet the surface of the respective adhesive base even at low pressure. This dosage form can be handled more easily than hot melt adhesives or liquid adhesive systems, requires no heating or other energy input during application and is generally free from chemical reactions after application.
Als acrylatbasierende Klebemasse im Sinne dieser Erfindung wird jede Klebemasse bezeichnet, die neben anderen optionalen Bestandteilen eine Basisklebemasse umfasst, deren klebtechnische Eigenschaften von einem Polymer bestimmt oder zumindest in nicht unwesentlichem Maß mitbestimmt werden, dessen Grundgerüst acrylatartige Monomere aufweist.For the purposes of this invention, the term "acrylate-based adhesive" refers to any adhesive which, in addition to other optional constituents, comprises a base adhesive whose adhesive properties are determined or at least to a considerable extent determined by a polymer whose backbone comprises acrylate-type monomers.
Es sind insbesondere Acrylathaftklebemassen als Selbstklebeschicht geeignet, die zumindest teilweise auf mindestens einem acrylartigen Monomer basieren. Vorteil der Acrylathaftklebemassen ist ihre hohe Transparenz sowie ihre gute thermische und Alterungsbeständigkeit.In particular, acrylate PSAs are suitable as self-adhesive layers which are based at least partly on at least one acrylic-type monomer. The advantage of acrylic PSAs is their high transparency and their good thermal and aging resistance.
Die Gruppe der acrylatartigen Monomere besteht aus sämtlichen Verbindungen mit einer Struktur, die sich von der Struktur von unsubstituierter oder substituierter Acrylsäure oder Methacrylsäure oder aber aus Estern dieser Verbindungen herleiten lässt, die sich durch die allgemeine Formel CH2=C(R1)(COOR2) beschreiben lassen, wobei der Rest R1 ein Wasserstoffatom oder eine Methylgruppe sein kann und der Rest R2 ein Wasserstoffatom sein kann oder aber aus der Gruppe der gesättigten, unverzweigten oder verzweigten, substituierten oder unsubstituierten C1- bis C30-Alkylgruppen gewählt ist. Vorzugsweise weist das Polymer der Basisklebemasse der acrylatbasierenden Klebemasse einen Gehalt an acrylatartigen Monomeren von 50 Gew.-% oder mehr auf.The group of acrylate-type monomers consists of all compounds having a structure which can be derived from the structure of unsubstituted or substituted acrylic acid or methacrylic acid or esters of these compounds represented by the general formula CH 2 = C (R 1 ) (COOR 2 ), where the radical R 1 can be a hydrogen atom or a methyl group and the radical R 2 can be a hydrogen atom or selected from the group of saturated, unbranched or branched, substituted or unsubstituted C 1 - to C 30 -alkyl groups is. The polymer of the base adhesive of the acrylate-based adhesive preferably has a content of acrylate-type monomers of 50% by weight or more.
Als acrylatartige Monomere sind grundsätzlich sämtliche der oben beschriebenen Gruppe dieser Verbindungen verwendbar, wobei deren konkrete Auswahl und deren Mengenverhältnisse sich gemäß den jeweiligen Anforderungen aus dem beabsichtigten Anwendungsbereich bemisst.In principle, all of the groups of these compounds described above can be used as acrylate-type monomers, their specific selection and their quantitative proportions being measured according to the respective requirements from the intended field of application.
Als Grundpolymer sind insbesondere solche acrylatbasierenden Polymere geeignet, die etwa durch radikalische Polymerisation erhältlich sind.Suitable base polymers are, in particular, those acrylate-based polymers which are obtainable, for example, by free-radical polymerization.
In einer weiteren vorteilhaften Ausführung ist das Heizelement dadurch gekennzeichnet, dass die Selbstklebemasse eine Styrolblockcopolymermasse ist. Dies hat den Vorteil, dass solche Massen auch auf unpolaren Untergründen gut kleben und daneben eine sehr gute Transparenz sowie bei hydrierten Polymertypen auch einen sehr gute Alterungsbeständigkeit aufweisen.In a further advantageous embodiment, the heating element is characterized in that the self-adhesive is a Styrolblockcopolymermasse. This has the advantage that such compositions stick well even on non-polar substrates and, in addition, have a very good transparency and, in the case of hydrogenated polymer types, also have very good resistance to aging.
Die Selbstklebemasse kann neben der Basisklebemasse selbstverständlich auch weitere Zusatzstoffe aufweisen wie zum Beispiel Füllstoffe, insbesondere nanoskalige Füllstoffe, die das Licht nicht streuen und somit die Transparenz erhalten, rheologische Additive, Additive zur Verbesserung der Haftung, Weichmacher, Harze, Elastomere, Alterungsschutzmittel (Antioxidantien), Lichtschutzmittel, UV-Absorber sowie sonstige Hilfs- und Zusatzstoffe, beispielsweise Fließ- und Verlaufsmittel und/oder Benetzer wie Tenside oder Katalysatoren.The self-adhesive may, of course, in addition to the base adhesive also other additives such as fillers, especially nanoscale fillers that do not scatter the light and thus obtain the transparency, rheological additives, additives to improve adhesion, plasticizers, resins, elastomers, anti-aging agents (antioxidants) , Light stabilizers, UV absorbers and other auxiliaries and additives, for example, flow and leveling agents and / or wetting agents such as surfactants or catalysts.
Weiterhin bevorzugt ist das Heizelement dadurch gekennzeichnet, dass die Selbstklebemasse eine Transparenz größer 70%, vorzugsweise größer 80%, besonders bevorzugt größer 90% aufweist. Dies ist beispielsweise bei einer Schichtdicke von 30 µm realisierbar. Die hohe Transparenz hat den Vorteil, dass das gesamte Heizelement eine erhöhte Transparenz aufweist. Neben der entsprechenden Auswahl der Polymere und Zusatzstoffe wird eine solch hohe Transparenz durch einen geringen Gelanteil (= partiell höher vernetzte Domänen, die das Licht streuen) in der Masse selbst sowie durch die Verwendung von sehr glattem Linermaterial, mit welchem die Selbstklebemasse nach der Beschichtung eingedeckt werden kann, erreicht. Mit letzterer Maßnahme erreicht man eine sehr glatte Oberfläche der Selbstklebeschicht, die das Licht weniger streut und reflektiert. Die Rauigkeit Rz beträgt demgemäß weniger als 0.5 µm, vorzugsweise weniger als 0.3 µm gemäß DIN EN ISO 4287.Further preferably, the heating element is characterized in that the self-adhesive composition has a transparency greater than 70%, preferably greater than 80%, especially preferably greater than 90%. This can be realized, for example, with a layer thickness of 30 μm. The high transparency has the advantage that the entire heating element has an increased transparency. In addition to the appropriate choice of polymers and additives such a high transparency is covered by a low gel content (= partially higher crosslinked domains that scatter the light) in the mass itself and by the use of very smooth liner material with which the self-adhesive composition after coating can be achieved. The latter measure achieves a very smooth surface of the self-adhesive layer, which scatters and reflects the light less. The roughness R z is accordingly less than 0.5 μm, preferably less than 0.3 μm in accordance with DIN EN ISO 4287.
Erfindungsgemäße Heizelemente können insbesondere für beheizbare Scheiben, seien sie aus Mineralglas oder aus Kunststoffglas wie etwa Plexiglas, vorzugsweise für ein Kraftfahrzeug, insbesondere auch für Außenrückspiegel, oder für ein Luftfahrzeug eingesetzt werden. Weitere Einsatzgebiete solcher Glasscheiben sind Helmvisiere oder Brillenverglasungen, z.B. für Skibrillen. In solchen und vielen anderen Anwendungsgebieten ist es vorteilhaft, die Transparenz des Heizelements zu begrenzen, da dieses dann gleichzeitig als Blendschutz wirken kann.Heating elements according to the invention can be used in particular for heatable panes, be they made of mineral glass or of plastic glass such as Plexiglas, preferably for a motor vehicle, in particular also for exterior rearview mirrors, or for an aircraft. Further fields of use of such glass panes are helmet visors or spectacle glazings, e.g. for ski goggles. In such and many other fields of application, it is advantageous to limit the transparency of the heating element, since this can then simultaneously act as a glare protection.
Daher weist eine weiterhin bevorzugte Ausführung des Heizelements eine Transparenz von höchstens 80 % auf. Dies kann z.B. durch Einfärbung von Trägermaterial und/oder Klebeschicht erreicht werden. Bevorzugt ist aber, den Typ der verwendeten Carbon-Nanotubes in der im Wesentlichen den Strom leitenden Schicht so auszuwählen, dass sich der gewünschte Transparenzgrad in dieser Schicht bei gleichzeitig ausreichender Heizfunktion einstellt. Dies hat den Vorteil, dass keine weiteren Maßnahmen in Trägermaterial und Kleberschicht zur Einstellung der Transparenz ergriffen werden müssen.Therefore, a further preferred embodiment of the heating element has a transparency of at most 80%. This can e.g. be achieved by coloring carrier material and / or adhesive layer. However, it is preferred to select the type of carbon nanotube used in the essentially the current-conducting layer so that the desired degree of transparency in this layer is established with sufficient heating function at the same time. This has the advantage that no further measures in carrier material and adhesive layer for adjusting the transparency must be taken.
Ferner ist in
Ferner ist in
In
Im Folgenden ist der Aufbau eines erfindungsgemäßen Heizelements anhand von Beispielen weiter erläutert.The structure of a heating element according to the invention is further explained below by means of examples.
Es wurde eine wässrige Dispersion von Carbon-Nanotubes hergestellt. Dabei wurde die Methode von Yerushalmi-Rozen et al. verwendet (
Als Carbon-Nanotubes wurden verwendet: ATI-MWNT-001 (Muli-walled CNT, unbundled as grown, 95 %ig, 3 bis 5 Schichten, mittlerer Durchmesser 35 nm, mittlere Länge 100 µm, Fa. Ahwahnee, San Jose, USA)As carbon nanotubes were used: ATI-MWNT-001 (Muli-walled CNT, unbound as grown, 95%, 3 to 5 layers, average diameter 35 nm, average length 100 microns, Fa. Ahwahnee, San Jose, USA)
Als Stabilisator wurde verwendet: PEO-b-PPO-b-PEO-Blockcopolymer mit einem Molgewicht Mn von 14.600 g/Mol (PEG = 80 % (G/G), Aldrich Nr. 542342). Der Stabilisator wurde in einer Konzentration von 1 Gew.-% in demineralisiertem Wasser gelöst.The stabilizer used was: PEO-b-PPO-b-PEO block copolymer having a molecular weight M n of 14,600 g / mol (PEG = 80% (w / w), Aldrich No. 542,342). The stabilizer was dissolved in a concentration of 1% by weight in demineralized water.
Es wurde dann eine 1 Gew.-% Dispersion von Carbon-Nanotubes in dieser Lösung hergestellt, wobei ein Ultraschallbad als Dispergierhilfe verwendet wurde. Nach vier Stunden Behandlung mit Ultraschall waren ca. 70 % der CNTs dispergiert (optische Abschätzung) und die Dispersion war bis zur weiteren Verarbeitung über mehrere Tage stabil. Die nicht dispergierten Nanotubes wurden abgefiltert.A 1 wt% dispersion of carbon nanotubes was then prepared in this solution using an ultrasonic bath as a dispersing aid. After four hours of ultrasound treatment, approximately 70% of the CNTs were dispersed (optical estimation) and the dispersion was stable for several days until further processing. The undispersed nanotubes were filtered off.
Die Dispersion wurde auf eine 23 µm dicke PET-Folie aufgerakelt und getrocknet, so dass sich eine trockene Schichtdicke von etwa 0.1 µm ergab.The dispersion was knife-coated onto a 23 μm thick PET film and dried to give a dry layer thickness of about 0.1 μm.
Es wurde dann eine etwa 20 µm dicke Schicht einer Acrylat-Haftklebemasse (acResin 258 von BASF, vernetzt mit 36 mJ/cm2) auf die leitfähige Schicht auflaminiert, wobei an den Rändern ein Streifen frei gelassen wurde. Dieser Bereich wurde sodann mit einem Streifen Silberleitlack bepinselt. Eine schematische Zeichnung dieses Heizelements zeigt
Das Heizelement zeigte bei einer angelegten Spannung von 12.8 V eine Aufheizrate von etwa 10°C/min und erreichte ausgehend von Raumtemperatur eine Gleichgewichtstemperatur von 39 °C, welche auf der Klebemasse gemessen wurde.The heating element showed at a voltage of 12.8 V applied a heating rate of about 10 ° C / min and reached, starting from room temperature, an equilibrium temperature of 39 ° C, which was measured on the adhesive.
Die Transmissionsmessung durch das Heizelement nach DIN 5036-3 ergab einen Transmissionsgrad τ von 63 %.The transmission measurement by the heating element according to DIN 5036-3 gave a transmittance τ of 63%.
Es wurde eine mit etwa 0.05 Gew.% (bezogen auf den Bindemittelanteil) Single-Walled-Carbon-Nanotubes gefüllte wässrige Bindemitteldispersion , die von der Fa. Eikos, Franklin, MA, USA, zu beziehen ist, auf eine 23 µm dicke PET-Folie aufgerakelt und getrocknet, so dass sich eine trockene Schichtdicke von etwa 0.5 µm ergab.An aqueous binder dispersion filled with about 0.05% by weight (based on the binder fraction) of single-walled carbon nanotubes, available from Eikos, Franklin, MA, USA, was applied to a 23 μm thick PET film. The film was knife-dried and dried to give a dry layer thickness of about 0.5 μm.
Es wurde dann eine etwa 20 µm dicke Schicht einer Acrylat-Haftklebemasse (acResin 258 von BASF, vernetzt mit 36 mJ/cm2) auf die leitfähige Schicht auflaminiert, wobei an den Rändern ein Streifen frei gelassen wurde. Dieser Bereich wurde sodann mit einem Streifen Silberleitlack bepinselt. Eine schematische Zeichnung dieses Heizelements zeigt
Das Heizelement zeigte bei einer angelegten Spannung von 12.8 V eine Aufheizrate von etwa 6°C/min und erreichte ausgehend von Raumtemperatur eine Gleichgewichtstemperatur von 28 °C, welche auf der Klebemasse gemessen wurde.The heating element showed at a voltage of 12.8 V applied a heating rate of about 6 ° C / min and reached, starting from room temperature, an equilibrium temperature of 28 ° C, which was measured on the adhesive.
Die Transmissionsmessung durch das Heizelement nach DIN 5036-3 ergab einen Transmissionsgrad τ von 72 %.The transmission measurement by the heating element according to DIN 5036-3 gave a transmittance τ of 72%.
Zu einer toluolischen Lösung enthaltend 20 Gew.-% einer Acrylat-Haftklebemasse (acResin 252 der Fa. BASF, Ludwigshafen) wurde eine Dispersion von 1 Gew.-% Single-Walled-Carbon-Nanotubes in Toluol der Fa. Zyvex im Verhältnis 5:1 gemischt, so dass sich ein Anteil von etwa 0.01 Gew.-% Carbon-Nanotubes bezogen auf die Acrylathaftklebemasse ergab.To a toluene solution containing 20 wt .-% of an acrylate PSA (acResin 252 Fa. BASF, Ludwigshafen) was a dispersion of 1 wt .-% single-walled carbon nanotubes in toluene from. Zyvex in the ratio 5: 1 mixed, so that a proportion of about 0.01 wt .-% carbon nanotubes based on the acrylic PSA resulted.
Die Dispersion wurde auf eine 23 µm dicke PET-Folie aufgerakelt und getrocknet, so dass sich eine trockene Schichtdicke von etwa 2 µm ergab. Diese Schicht wurde mittels UV-Strahlung mit einer UV-C-Dosis von 36 mJ/cm2 mittels eines Mitteldruck-Quecksilberstrahlers vernetzt.The dispersion was knife-coated onto a 23 μm thick PET film and dried to give a dry layer thickness of about 2 μm. This layer was crosslinked by means of UV radiation with a UV-C dose of 36 mJ / cm 2 by means of a medium-pressure mercury radiator.
Es wurde dann eine etwa 20 µm dicke Schicht einer Acrylat-Haftklebemasse (acResin 258 von BASF, vernetzt mit einer UV-C-Dosis von 36 mJ/cm2) auf die leitfähige Schicht auflaminiert, wobei an den Rändern ein Streifen frei gelassen wurde. Dieser Bereich wurde sodann mit einem Streifen Silberleitlack bepinselt. Eine schematische Zeichnung dieses Heizelements zeigt
Das Heizelement zeigte bei einer angelegten Spannung von 12.8 V eine Aufheizrate von etwa 15°C/min und erreichte ausgehend von Raumtemperatur τ eine Gleichgewichtstemperatur von 45 °C, welche auf der Klebemasse gemessen wurde.The heating element showed at a voltage of 12.8 V applied a heating rate of about 15 ° C / min and reached from room temperature τ an equilibrium temperature of 45 ° C, which was measured on the adhesive.
Die Transmissionsmessung durch das Heizelement nach DIN 5036-3 ergab einen Transmissionsgrad τ von 59 %.The transmission measurement by the heating element according to DIN 5036-3 gave a transmittance τ of 59%.
Claims (24)
- Heating element having a current conductor,
where electrical current can be conducted substantially through the current conductor and where, as a result of a drop in voltage at an ohmic resistor, current can be converted into heat,
where the heating element is designed as a planar structure or tapelike structure and has at least one backing layer (1) and an adhesive layer (3), where the current conductor is designed as an additional layer: current-conducting layer (2), where the current-conducting layer (2) is disposed between the backing layer (1) and the adhesive layer (3), and
characterized in that
the backing layer (1), the current-conducting layer (2), and the adhesive layer (3) are transparent and the current-conducting layer (2) comprises carbon nanotubes. - Heating element according to Claim 1, characterized
in that the current-conducting layer (2) is designed such that at least 90%, preferably at least 95%, more preferably at least 98% of the current flowing overall through the heating element flows through the current-conducting layer (2). - Heating element according to either of the preceding claims, characterized in that
the heating element has regions with different heating power,
preferably in that the current-conducing layer (2) has a regionally different concentration of carbon nanotubes and/or a regionally different thickness. - Heating element according to Claim 3, characterized
in that the carbon nanotubes are embedded in a transparent matrix. - Heating element according to Claim 4, characterized
in that the transparent matrix has a polymeric binder,
where, preferably, the polymeric binder is converted into the current-conducting layer (2) from a solution or dispersion in one or more organic solvents or in water. - Heating element according to Claim 5, characterized
in that the monomers serving to prepare the matrix material are selected such that the resulting polymers can be used as pressure-sensitive adhesives at room temperature or higher temperatures. - Heating element according to any of Claims 4 to 6, characterized
in that the matrix material is a pressure-sensitive acrylate adhesive. - Heating element according to any of the preceding claims, characterized
in that two surface regions are provided which are designed for introduction of current into the current-conducting layer (2) and
in that in the surface regions there is either no adhesive layer (3) disposed on the current-conducting layer (2) and/or there is a different kind of electrically conductive layer (5) disposed, said layer (5) having an electrical conductivity which is at least 10 times higher than that of the current-conducting layer (2). - Heating element according to any of the preceding claims, characterized in that two further transparent layers (5) are disposed above and below the current-conducting layer, and are likewise electrically conductive, said layers (5) having an electrical conductivity which is at least 10 times higher than that of the current-conducting layer (2).
- Heating element according to any of the preceding claims, characterized in that the carbon nanotubes have an average length of at least 10 µm.
- Heating element according to any of the preceding claims, characterized in that the carbon nanotubes have an average outer diameter of less than 40 nm.
- Heating element according to any of the preceding claims, characterized in that the carbon nanotubes have an average ratio of length to outer diameter of at least 250.
- Heating element according to any of the preceding claims, characterized in that the surface of the carbon nanotubes is chemically modified.
- Heating element according to any of the preceding claims, characterized in that the carbon nanotubes are single-walled carbon nanotubes.
- Heating element according to any of Claims 1 to 13, characterized
in that the carbon nanotubes are multi-walled carbon nanotubes. - Heating element according to any of the preceding claims, characterized in that at least some, preferably a majority, of the carbon nanotubes within the current-conducting layer (2) are oriented in a preferential direction.
- Heating element according to any of the preceding claims, characterized in that the current-conducting layer (2), in addition to the carbon nanotubes, has further conductive components, preferably intrinsically conductive polymers.
- Heating element according to any of the preceding claims, characterized in that the adhesive layer (3) is designed as a self-adhesive layer.
- Heating element according to Claim 18, characterized
in that the self-adhesive is an acrylate adhesive. - Heating element according to Claim 18, characterized
in that the self-adhesive is a styrene block copolymer adhesive. - Heating element according to any of Claims 18 to 20, characterized in that the self-adhesive has a transparency of greater than 70%, preferably greater than 80%, more preferably greater than 90%.
- Heating element according to any of the preceding claims, characterized in that the layer (2) which substantially conducts the current has a transparency of not more than 80%.
- Heatable pane with a heating element, especially for a motor vehicle or aircraft,
characterized
in that the heating element is designed in accordance with any of Claims 1 to 22. - Heatable pane according to Claim 23, characterized in that the pane is composed of mineral glass or plastic glass, especially Plexiglas.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102007004953A DE102007004953A1 (en) | 2007-01-26 | 2007-01-26 | heating element |
PCT/EP2008/050248 WO2008090031A1 (en) | 2007-01-26 | 2008-01-10 | Heating element, and heatable pane comprising a heating element |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2127476A1 EP2127476A1 (en) | 2009-12-02 |
EP2127476B1 true EP2127476B1 (en) | 2014-01-01 |
Family
ID=39415227
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08701394.2A Active EP2127476B1 (en) | 2007-01-26 | 2008-01-10 | Heating element, and heatable pane comprising a heating element |
Country Status (9)
Country | Link |
---|---|
US (1) | US9332593B2 (en) |
EP (1) | EP2127476B1 (en) |
JP (1) | JP2010517231A (en) |
KR (1) | KR20090107553A (en) |
CN (1) | CN101601328B (en) |
DE (1) | DE102007004953A1 (en) |
ES (1) | ES2445396T3 (en) |
TW (1) | TW200843544A (en) |
WO (1) | WO2008090031A1 (en) |
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-
2007
- 2007-01-26 DE DE102007004953A patent/DE102007004953A1/en not_active Withdrawn
-
2008
- 2008-01-10 US US12/523,583 patent/US9332593B2/en active Active
- 2008-01-10 JP JP2009546709A patent/JP2010517231A/en not_active Withdrawn
- 2008-01-10 ES ES08701394.2T patent/ES2445396T3/en active Active
- 2008-01-10 CN CN200880003214.7A patent/CN101601328B/en active Active
- 2008-01-10 EP EP08701394.2A patent/EP2127476B1/en active Active
- 2008-01-10 WO PCT/EP2008/050248 patent/WO2008090031A1/en active Application Filing
- 2008-01-10 KR KR1020097017791A patent/KR20090107553A/en not_active Application Discontinuation
- 2008-01-24 TW TW097102618A patent/TW200843544A/en unknown
Also Published As
Publication number | Publication date |
---|---|
TW200843544A (en) | 2008-11-01 |
US9332593B2 (en) | 2016-05-03 |
CN101601328A (en) | 2009-12-09 |
US20100059494A1 (en) | 2010-03-11 |
ES2445396T3 (en) | 2014-03-03 |
DE102007004953A1 (en) | 2008-07-31 |
CN101601328B (en) | 2014-07-02 |
KR20090107553A (en) | 2009-10-13 |
EP2127476A1 (en) | 2009-12-02 |
JP2010517231A (en) | 2010-05-20 |
WO2008090031A1 (en) | 2008-07-31 |
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