EP3475958B1 - Electrically conductive shaped body with a positive temperature coefficient - Google Patents
Electrically conductive shaped body with a positive temperature coefficient Download PDFInfo
- Publication number
- EP3475958B1 EP3475958B1 EP17736583.0A EP17736583A EP3475958B1 EP 3475958 B1 EP3475958 B1 EP 3475958B1 EP 17736583 A EP17736583 A EP 17736583A EP 3475958 B1 EP3475958 B1 EP 3475958B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- copolymer
- weight
- temperature
- ethylene
- change material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
- H01C7/028—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient consisting of organic substances
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/006—Apparatus or processes specially adapted for manufacturing resistors adapted for manufacturing resistor chips
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
- H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
- H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
- H01C17/06573—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the permanent binder
- H01C17/06586—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the permanent binder composed of organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
- H01C7/027—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient consisting of conducting or semi-conducting material dispersed in a non-conductive organic material
Definitions
- the present invention relates to electrically conductive moldings, as specified in claim 1, made from an electrically conductive polymer composition with an inherent positive temperature coefficient (PTC), at least one organic matrix polymer, submicron or nanoscale, electrically conductive particles and at least one phase change material with a phase transition temperature in the range from -42 °C to + 150 °C.
- PTC inherent positive temperature coefficient
- the shaped bodies are created in the injection molding process and are electrically conductive monofilaments, multifilaments, fibers or nonwovens that can be used, for example, in car seat heaters or electric blankets or technical textiles and regulate the flow of electricity themselves.
- Polymeric PTC compositions consist of a mixture of organic polymers, in particular crystalline and partially crystalline polymers, and electrically conductive additives.
- the PTC effect is mostly based on a structural change in crystalline polymer domains towards less crystalline or amorphous areas when the temperature increases.
- special polymer blends include thermoelastic polymers, resins and other elastomers. An example of this is in WO2006115569 described.
- Such polymer compositions have the disadvantage that the PTC effect is limited to a switching behavior that is based on structural changes in the polymers used as the main component.
- the PTC intensity ie the Change in resistance very much dependent on the polymer or polymer blend used.
- liquid polymer dispersions with a PTC effect which are provided for coatings or paintwork, are known in the prior art.
- the PTC effect is based on an additive such as paraffin or polyethylene glycol (PEG), see eg WO 2006/006771 .
- JP 2012-181956 A discloses an aqueous dispersion paint containing an acrylic ester copolymer, a crystalline thermosetting resin, paraffin, carbon black and graphite as an electrically conductive material, and a crosslinking agent.
- the thermosetting resin is preferably a polyethylene glycol
- the crosslinking agent is preferably a polyisocyanate.
- the paint is applied to a surface and heated to a temperature of 130 to 200 °C for 30 to 60 minutes. This creates a coating with a PTC effect that can serve as surface heating.
- impregnation and coating compositions are problematic since solvents frequently outgas in an uncontrolled manner during application, with more or less visible craters and bubbles forming in the coating. If the substrate to be coated is insufficiently pre-treated, the surface energy is too small or too large, and the surface structure is unsuitable, the adhesion of the coating is often poor. The result is flaking and flaking of the functional layer and, associated with this, a significant impairment of the electrical conductivity and the PTC effect. Incorrect application of the impregnation or coating composition, insufficient drying and/or crosslinking, drying or curing temperatures and times that are too high or an overdose of crosslinking radiation directly impair the durability and functionality of the coating. This applies in particular, but not only, to the coating of textiles. In addition, there is often partial or large-area "bleeding" of paraffin from such impregnations and coatings, so that these fail after a short period of operation.
- an organic PTC thermistor comprising a matrix of at least two polymers, a low molecular weight organic compound and electrically conductive metal particles, the surface of each particle having 10 to 500 conical projections. About 10 to 1,000 of these particles can be connected in the form of a network to form a secondary particle.
- the individual particles preferably consist of nickel. They have an average diameter of about 3 to 7 ⁇ m. At least one of the two polymers in the matrix must be a thermoplastic elastomer.
- the thermoplastic elastomer ensures the reproducibility of the electrical properties of the PTC composite material, in particular a low electrical resistance at room temperature and a high resistance change at elevated temperatures, even when the low molecular weight organic compound melts.
- the low molecular weight organic compound is preferably a paraffin wax with a melting point between 40 and 200°C.
- Further electrically conductive particles can be contained in the matrix, for example those made of carbon black, graphite, carbon fibers, tungsten carbide, titanium nitride, carbide or boride, zirconium nitride or molybdenum silicide.
- the PTC thermistor can be formed by pressing at an elevated temperature (e.g. at 150°C) or by applying a mixture which also contains a solvent such as toluene onto a support such as nickel foil and then heating and curing the resulting coating.
- WO 2006/006771 A1 describes an aqueous electrically conductive polymer composition which has a positive temperature coefficient (PTC). It contains a water-soluble polymer, a paraffin and electrically conductive carbon black.
- the water soluble polymer is preferably polyethylene glycol.
- a coating which can be used as surface heating can be produced with the aqueous composition.
- compositions for electrically conductive polymer moldings with PTC within the meaning of this invention comprise a matrix polymer, a conductivity additive and a phase change material as essential components.
- the processing temperature in melt processes is usually in the range from 100°C to over 400°C, in particular in the range from 105°C to 450°C. At these temperatures, the phase change material liquid and has a low viscosity. In contrast, the plasticized matrix polymer has a much higher, z. T. higher viscosity by several orders of magnitude.
- phase change material is present as a phase intercalated in the matrix polymer. Due to the high mechanical load or the high shear stress or the pressure at extruder or injection molding nozzles in connection with the temperature, which is well above the melting range of the phase change material, the intercalated low-viscosity phase change material is displaced from the matrix polymer and partially discharged into the environment. In addition, this effect can be intensified in certain temperature/shear stress/pressure ranges by deformation-induced phase segregation or demixing.
- the loss of phase change material is particularly high when the extruded shaped body, such as a fiber or film, has small dimensions of less than 1000 ⁇ m in at least one spatial direction.
- the loss of phase change material is also referred to by the term “bleeding out”.
- phase change material is heated and liquefied during the intended use of the PTC molded body, the PTC molded body z. T. is exposed to considerable mechanical stress. Phase change material therefore "bleeds out” even when the PTC molded body is used.
- the moldings of the present invention are intended in particular for electrically heatable sheetlike structures, such as foils, textile fibers and/or nonwovens.
- a heating power P of a few watts up to about 2000 W is to be provided.
- the heating output is limited by the available voltage U and the resistance R of the shaped body.
- the voltage available for stationary or portable applications is in the range of 1.5 to 240 V.
- the electrical resistance R of the shaped body should be in the range from 1 to 200 ⁇ .
- the specific resistance ⁇ of a conductive shaped body is determined by the content and the electrical conductivity of the conductivity additive.
- the specific resistance required for the heating applications discussed above can be achieved by means of a correspondingly high content of conductivity additive.
- the associated costs and/or the impairment of the mechanical properties of the molded body represent a significant obstacle for many applications.
- the conductivity additive in the polymer matrix must form a conductive network with a suitable morphology.
- the proportion of the conductivity additive must not exceed a specific value in order not to impair the mechanical properties of the shaped body, such as elongation at break, too severely.
- the object of the present invention was to overcome the problems that existed up to now and to provide a composition from which electrically conductive shaped bodies with an inherent PTC effect can be produced.
- the anhydrous composition should be capable of being processed into shaped articles using conventional melting processes, such as extrusion, melt spinning or injection molding.
- moldings can be produced in a melting process if submicro- or nanoscale, electrically conductive particles form a thermoplasticizable mixture together with a phase change material, which is advantageously combined in polymer network structures of a copolymer to form a masterbatch, and with other compound components.
- a molded body made from an electrically conductive composition with an inherent positive temperature coefficient which contains at least one organic matrix polymer (compound component A), submicroscale or nanoscale, electrically conductive particles (compound component B) and at least one phase change material with a Phase transition temperature in the range from - 42 °C to + 150 °C (compound component D) and optionally stabilizers, modifiers, dispersants and processing aids, the polymer composition having a melting range in the interval from 100 to 450 °C, characterized in that the Phase change material is integrated into an organic network of at least one copolymer based on at least two different ethylenically unsaturated monomers (compound component C), as well as the setting of the temperature range for d as the onset of the PTC effect is realized and the PTC effect results from the increase in volume of the phase change material as a result of the temperature increase, the electrically conductive molded bodies do not experience any changes in the morphology of the crystalline structures when the PTC
- a temperature increase of 60 °C leads to an increase in the PTC intensity of 50% or more.
- Such a temperature increase preferably leads to an increase in the PCT intensity by at least 75%, particularly preferably by at least 100%, as also shown in the examples below.
- the temperature change can be repeated as often as desired without the morphology in the crystalline areas of the shaped body changing as a result.
- the phase change material can be mixed with the other components in pure form or in the form of a masterbatch.
- the composition consists of 10 to 90% by weight matrix polymer, 0.1 to 30% by weight of electrically conductive particles, 2 to 50% by weight Phase change material with a phase transition temperature in the range from -42 °C to 150 °C, 0 to 10% by weight of processing aids and stabilizers, modifiers and dispersing agents, based on the total weight of the composition, the sum of the parts by weight of all components of the composition being 100% by weight -% and the composition has a melting range in the interval 100°C to 450°C.
- the shaped body according to the invention is a monofilament, multifilament, fiber or fleece.
- Monofilaments preferably have an average diameter of 8 to 400 ⁇ m, 80 to 300 ⁇ m, in particular 100 to 300 ⁇ m.
- Multifilaments expediently consist of 8 to 48 individual filaments. the individual filaments preferably having an average diameter of 8 to 40 ⁇ m.
- the shaped body according to the invention has a specific electrical resistance p(T) at a temperature (T) above the phase transition temperature of the phase change material which is 1.1 to 30 times, preferably 1.5 to 21 times, particularly preferably that 3 to 10 times the electrical resistivity at a temperature below the phase transition temperature.
- Another object of the invention is to provide electrically heatable textiles. This problem is solved by a textile that contains monofilaments, multifilaments,
- Fibers, or fleece of the composition described above contains.
- phase change material denotes a single substance as well as a composition of two or more substances, wherein the individual substance or at least one substance of the composition has a phase transition temperature in a range from -42 °C to +150 °C .
- the phase transition is preferably a solid-to-liquid transition, i.e. the phase change material preferably has a major melting peak in the range of -42°C to +150°C.
- the phase change material consists, for example, of a paraffin or a composition comprising a paraffin and one or more polymers, the polymers binding and stabilizing the paraffin.
- microscale and “nanoscale” refer to particles and bodies which have a dimension of less than 1000 nm or 100 nm or less in at least one spatial direction. Accordingly, particles or flakes which have a dimension of 300 to 800 nm in a spatial direction, for example, are referred to as “microscale”. In contrast, particles or fibers which, for example, have a dimension of 10 to 50 nm in one spatial direction are referred to as “nanoscale”.
- the composition contains at least one thermoplastic organic polymer or crosslinkable copolymer, a conductive filler, and phase change materials, as well as other inert or functional materials. The material combination is selected specifically for the desired application.
- Suitable phase change materials are selected to adjust the PTC switching behavior at different transition temperatures. These materials are preferably introduced into polymeric network structures before use in the matrix polymer or in the matrix polymer blend itself and/or their viscosity behavior can be influenced by additives. These phase change materials modified in this way are intensively mixed into the matrix polymer or the matrix polymer blend together with the conductive additives, resulting in a largely homogeneous distribution of the conductivity additives and the phase change materials. The polymer composition then has a PTC effect.
- inert or functional additives can be added to the composition according to the invention, such as for example thermal and/or UV stabilizers, oxidation inhibitors, adhesion promoters, dyes and pigments, crosslinking agents, processing aids and/or dispersing aids.
- agents and fillers in particular silicon carbide, boron nitride and/or aluminum nitride, can also be added to increase thermal conductivity.
- the matrix polymer or the matrix polymer blend - hereinafter referred to as compound component A - contains one or more crystalline, semi-crystalline and/or amorphous polymers from the group of polyethylenes (PE) such as LDPE, LLDPE, HDPE and/or the respective copolymers from the group of atactic, syndiotactic and/or isotactic polypropylenes (PP) and/or the respective copolymers from the group of polyamides (PA), including in particular PA-11, PA-12, the PA-6.66 copolymers, the PA-6.10 copolymers , the PA-6.12 copolymers, PA-6 or PA-6.6, from the group of polyesters (PES) with aliphatic, with aliphatic in combination with cycloaliphatic and/or with aliphatic in combination with aromatic components, including in particular polybutylene terephthalate (PBT) , polytrimethylene terephthalate (PTT) and polyethylene terephthalate (
- the conductivity additive contained in the composition is in the form of microscale or nanoscale domains, microscale or nanoscale particles, microscale or nanoscale fibers, microscale or nanoscale needles, microscale or nanoscale tubes and/or microscale or nanoscale platelets and consists of one or more conductive polymers, carbon black, conductive carbon black, graphite, expanded graphite, single-walled and/or multi-walled carbon nanotubes (CNT), open and/or closed carbon nanotubes, empty and/or or carbon nanotubes, graphene, carbon fibers (CF), flakes and/or particles of a metal such as Ni, Ag, W, Mo, Au, Pt, Fe, Al, Cu filled with a metal such as silver, copper or gold , Ta, Zn, Co, Cr, Ti, Sn or alloys of two or more metals.
- a metal such as Ni, Ag, W, Mo, Au, Pt, Fe, Al, Cu filled with a metal such as silver, copper or gold , Ta, Zn, Co, Cr, Ti
- the conductivity additive or the compound component B also includes a polymer in which the conductive particles are dispersed, so that the compound component B in the Production of moldings can be used as a masterbatch.
- a phase change material (compound component D) is bound into a polymeric network of a compound component C.
- Compound component C contains one or more polymers from the group of terblock polymers consisting of styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), tetra-block polymers consisting of styrene-ethylene-butylene-styrene (SEBS) , from styrene-ethylene-propylene-styrene (SEPS), from styrene-poly(isoprene-butadiene)-styrene (SIBS), from terblock polymers consisting of ethylene-propylene-diene (EPDM), from terpolymers consisting of ethylene, vinyl acetate and vinyl alcohol (EVAVOH), from ethylene, methyl and/or ethyl and/or propyl and/or butyl acrylate and maleic anhydride (EAEMSA), from ethylene, methyl and/or eth
- EAE Ethylene and acrylic acid esters
- EAE Ethylene and acrylic acid esters
- PE polyethylenes
- LDPE low density polyethylene
- LLDPE low density polyethylene
- HDPE high density polyethylene
- graft copolymers of Polyethylene from the group of atactic, syndiotactic and / or isotactic polypropylenes (PP) and / or the respective copolymers, including the graft copolymers of polypropylene originate.
- copolymer also includes terpolymers and polymers with units made up of 4 or more different monomers.
- a masterbatch which contains the conductivity additive (compound component B) and the phase change material (compound component D) dispersed in the compound component C.
- a polymeric modifier is expediently added to the composition, which improves the thermoplastic properties and the processability.
- the polymeric modifier is preferably selected from the group comprising amorphous polymers such as cycloolefin copolymers (COC), amorphous polypropylene, amorphous polyamides, amorphous polyesters or polycarbonates (PC).
- phase change material or the Compound component C added a micro- or nanoscale stabilizer.
- nanoscale materials includes additives that are in the form of a powder, a dispersion or a polymer composite and contain particles that are less than 100 nanometers in at least one dimension, in particular the thickness or diameter.
- lipophilic, hydrophobic layered minerals e.g. B. lipophilic phyllosilicates, including lipophilic bentonites, which exfoliate in plasticizing and mixing processes during processing of the composition according to the invention.
- These exfoliated particles generally have a length and width of about 200 nm to 1000 nm and a thickness of about 1 nm to 4 nm.
- the ratio of length and width to thickness is preferably about 150 to 1000, preferably 200 to 500
- Further hydrophobic viscosity-increasing agents that are preferably used are hydrophobicized nanoscale pyrogenic silicas. These nanoscale fumed silicas generally consist of particles with an average diameter of preferably 30 nm to 100 nm.
- a lubricant is used to adjust the melt viscosity.
- the lubricant can be added to the phase change material or to compound component C.
- the composition according to the invention contains a phase change material (phase change material or PCM), also referred to as compound component D here.
- phase change material phase change material or PCM
- the phase change material has a phase transition temperature in the range from -42° C. to +150° C., in particular from -30° C. to +96° C., at which its volume or its density changes reversibly.
- Phase change material within the meaning of this invention are all materials selected from the groups mentioned in the previous paragraph, which have a phase transition temperature in the range from -42 °C to +150 °C, in particular from -30 °C to +96 °C, at which their volume or their density changes reversibly.
- phase change materials can be used alone (in raw form), as materials integrated into a polymer network or as mixtures of these two forms.
- Polyester alcohols, polyether alcohols or polyalkylene oxides, for example are suitable as phase change materials in raw form.
- the phase change materials are used bound in a polymer network.
- This polymer network is formed from at least one copolymer based on at least two different ethylenically unsaturated monomers (compound component C).
- a polymeric modifier is expediently added to the composition, which improves the thermoplastic properties and the processability.
- the polymeric modifier is selected from the group comprising amorphous polymers such as cycloolefin copolymers (COC), polymethyl methacrylate (PMMA), amorphous polypropylene, amorphous polyamide, amorphous polyester or polycarbonate (PC).
- the composition contains one or more additive(s), referred to below as compound component E, which are selected from the group of flame retardant substances and/or thermal and/or UV-Vis light stabilizers and/or oxidation inhibitors and/or or the ozone inhibitors and/or the dyes and/or dyes and/or other pigments and/or the foam generators and/or the adhesion promoters and/or the processing aids and/or the crosslinking agents and/or the dispersing aids and/or the other agents and Fillers, in particular silicon carbide, boron nitride and/or aluminum nitride to increase thermal conductivity.
- additives referred to below as compound component E
- compound component E which are selected from the group of flame retardant substances and/or thermal and/or UV-Vis light stabilizers and/or oxidation inhibitors and/or or the ozone inhibitors and/or the dyes and/or dyes and/or other pigments and/or the foam generators and/or the adhesion promoter
- the composition expediently contains, based on its total weight, 10 to 98% by weight of matrix polymer or matrix polymer blend and a total of 2 to 90% by weight of conductivity additive and phase change material and optionally further additives. It preferably contains 15 to 89% by weight of matrix polymer or matrix polymer blend and a total of 11 to 85% by weight of conductivity additive and phase change material and optionally other additives.
- the composition particularly preferably contains 17 to 50% by weight of matrix polymer or matrix polymer blend and a total of 50 to 83% by weight of conductivity additive and phase change material and optionally further additives.
- the temperature range and the intensity of the PTC effect of the moldings produced from the composition can be adapted to the application requirements by selecting the components and their respective mass fraction.
- moldings such as monofilaments, multifilaments, staple fibers, closed-cell or open-cell or mixed-cell foams, integral foams, small and large-area layers, patches, films or foils can be produced from the composition.
- the moldings produced from the composition are crosslinked with the aid of crosslinking agents and/or by the action of heat and/or high-energy radiation in order to permanently stabilize the electrical and thermal properties.
- Molded articles such as monofilaments, multifilaments, staple fibers, spunbonded nonwovens, closed-cell or open-celled or mixed-cell foams, integral foams, small and large-area layers, patches, films, foils or injection-molded articles can be produced by thermoplastic processing processes, which have a positive temperature coefficient of electrical resistance or PTC have effect.
- thermoplastic processing processes which have a positive temperature coefficient of electrical resistance or PTC have effect.
- products can be produced whose electrical resistance increases significantly when a predetermined electrical voltage U in the range from 0.1 V to 240 V is applied with increasing temperature in a defined temperature range, which reduces the current and the electrical power consumed in the product is limited.
- the temperature range and the intensity of the PTC effect can be adjusted by varying the compound components A, B, C, D and, if applicable, E.
- the figures document this behavior Fig. 1a such as Fig. 1b .
- Fig. 1a is the electric current strength I and in the Fig. 1b the temperature T each as a function of time for a reproduced "self-regulating" heating fabric.
- the "self-regulating" heating fabric was produced using a PTC monofilament according to the invention with a diameter of 300 ⁇ m as weft thread in a carrier fabric made from polyester multifilaments. With the heating fabric, a heating output of 248 watts per square meter can be generated by applying a voltage of 24 volts.
- Part of the heat generated in the heating fabric is dissipated to the environment by thermal radiation and convection.
- the heat remaining in the heating fabric causes a steady temperature increase, especially in the PTC filaments.
- the temperature of the heating fabric is also constant.
- Fig. 1b shows the temperature of this specific heating fabric as a function of time. With an applied voltage of 24 V or 30 V, the temperature in thermal equilibrium is at values of 63 °C or 59 °C.
- mono- and multi-filaments can be produced with different PTC characteristics or resistance-temperature characteristics.
- the monofilaments designated "PTC-Monofilament_01a” and “PTC-Monofilament_01b” contain a phase change material (PCM) with a melting range of 45 °C to 63 °C and a main melting peak at a temperature of 52 °C. The proportion of the phase change material was 5.25% by weight.
- PCM phase change material
- the two curves (a) and (b) demonstrate the good reproducibility of the manufacturing process.
- “PTC-Monofilament_01a” and “PTC-Monofilament_01b” come from different filament spools, the deviation between curves (a) and (b) is negligible.
- phase change material with a main melting peak at a temperature of 35 °C and 28 °C, respectively was used in the monofilaments designated "PTC-Monofilament_02" and “PTC-Monofilament_03".
- the PTC effect can therefore be observed in both monofilaments at correspondingly low temperatures compared to "PTC-Monofilament_01".
- the same phase change material as in the case of sample "PTC-Monofilament_01" was used, each with a weight proportion of 5.25% by weight, i.e. H.
- the monofilaments "PTC-Monofilament_05”, “PTC-Monofilament_04” and “PTC-Monofilament_07” differ in their electrical conductivity, since the type, composition and proportion of the conductivity component B varies in each case. This has a significant impact on the initial level of electrical resistance of the filaments at 24 °C.
- the sample with the designation "PTC-Multifilament_06” is a multifilament with a fineness of 307 dtex f36. A material was chosen for its production which, due to the type and proportion of the conductivity component B, leads to a relatively good specific electrical conductivity and at the same time allows the production of multifilaments.
- the electrical resistance of the multifilament yarn "PTC-Multifilament_06" was 13.1 M ⁇ /m and was therefore comparatively low compared to the monofilaments with a fineness of 760 dtex and a diameter of 300 ⁇ m.
- the PTC intensity of the multifilament yarn essentially corresponded to the behavior observed with monofilaments.
- the possible uses and applications of the moldings according to the invention with PTC are diverse, since they can be charged with low voltages from 0.1 volts to 42 volts as well as with relatively high electrical voltages of up to 240 volts, as well as with direct or alternating voltage and frequencies of up to 1 megahertz and permanently stable electrical and have thermal properties.
- Carbon black is preferably used as the conductivity additive.
- the terms “soot” and “carbon black” are used synonymously.
- Carbon black is manufactured using a variety of processes. Depending on the manufacturing process or starting material, the carbon black obtained is also referred to as "Furnace Black”, “Acetylene Black”, “Plasma Black” or “Activated Carbon”.
- Carbon black consists of so-called primary soot particles with an average diameter in the range of 15 to 300 nm. Due to the manufacturing process, a large number of primary soot particles form a so-called soot aggregate in which neighboring primary soot particles are connected to one another by mechanically very stable sinter bridges. Due to electrostatic attraction, the carbon black aggregates form more or less strongly bound agglomerates. Depending on the supplier of the carbon black, the soot aggregates and agglomerates may also be granulated or pelletized.
- the carbon black aggregates and agglomerates are subjected to shear forces.
- the maximum shear force acting in a polymeric melt depends in a complex manner on the geometry and operating parameters of the extruder or gelling unit used, as well as on the rheological properties of the polymeric composition and its temperature.
- the maximum shear force experienced in the melt process can exceed the electrostatic binding force and break down carbon black agglomerates into carbon black aggregates that are dispersed in the melt.
- increased agglomeration or flocculation can occur in low-viscosity polymer melts or solutions with high mobility of the carbon black aggregates and low shearing force.
- the conductivity of a polymer molding containing carbon black is decisively influenced by the proportion and the distribution and morphology of the carbon black agglomerates and aggregates.
- the distribution and morphology of carbon black in a melt-processed polymer molding depends on the nature of the carbon black additive, the rheological properties of the polymer composition, and the process parameters.
- the process parameters must be suitably adjusted in such a way that the shaped body has the specified conductivity.
- the influence and the interaction between the physical properties of the carbon black additive, the other components of the polymer composition and the process parameters is extremely complex and up to now only insufficiently understood.
- the phase change material can comprise one or more substances.
- the phase change material comprises a compound component C that functions as a network former and stabilizer, and a compound component D that is a substance, in particular a paraffin, with a phase change in a temperature range from about 20° C. to about 100° C. Percentages are percentages by weight unless otherwise stated or immediately apparent from the context.
- the matrix polymer or compound component A consists of a mixture with a proportion of 39.8% by weight of polypropylene of the Moplen ® 462 R type and low-density polyethylene (LDPE) of the Lupolen ® type with a proportion of 22.5% by weight. -% and as A conductive carbon black of the “Super Conductive Furnace N 294” type was used as conductivity additive or compound component B with a proportion of 22.5% by weight.
- Compound component C consisted of a blend of styrene block copolymer and poly(methyl methacrylate), each with a proportion of 2.25% by weight. 10.5% by weight of Rubitherm RT52 paraffin with a main melting peak at a temperature of 52° C.
- PCM granules the matrix polymers polypropylene ( Moplen® 462 R) in granular form and polyethylene (LDPE Lupolen® ) in granular form and compound component E were mixed together and placed in an extruder hopper.
- the conductive carbon black or the compound component B was placed in a metering device connected to the extruder.
- the dosing device enables the conductive carbon black to be introduced uniformly into the polymer melt.
- the extruder is a Haake Rheomex PTW 16/25 co-rotating twin screw extruder with a standard configuration, ie with segmented screws without return elements.
- the contents of the hopper and the conductive carbon black were plasticized, homogenized and extruded with the extruder.
- the hopper extruder and the dosing device were flooded with nitrogen.
- the screw speed was 180 rpm and the mass throughput was about 1 kg/h.
- the temperature of the extruder zones was as follows: 220°C at the feed, 240°C in zone 1, 260°C in zone 2, 240°C in zone 3 and 220°C at the strand die.
- the inside diameter of the strand die was 3 mm.
- the extruded and cooled polymer strand was granulated in a granulator.
- the polymer granules obtained in this way had the following composition: - 39.8% by weight polypropylene as part of compound component A; - 22.5% by weight Low density polyethylene (LDPE) as part of compound component A; - 22.5% by weight conductive carbon black as compound component B; - 15.0% by weight PCM granules with 10.5% by weight of paraffin as compound component D and 2.25% by weight each of SEEPS and PMMA as compound component C; - 0.2% by weight Additives as compound component E.
- LDPE Low density polyethylene
- the mass throughput of polymer melt was 13.7 g/min.
- the following melt temperature regime was implemented: 200 °C in zone 1, 210 °C in zone 2, 220 °C in zone 3, 230 °C in zone 4, 240 °C in zone 5, 250 °C in zone 6 and 260 °C C at the filament nozzle.
- the nozzle hole diameter was 1 mm.
- the extruded polymer melt was cooled in a water bath at a temperature of 20° C. and the solidified monofilament was stretched “online” with three stretching units in one process step.
- the peripheral speed of the godets of the first stretching unit was 58.2 m/min and that of the second stretching unit was 198 m/min.
- a stretching bath arranged between the first and second stretching units contained water at a temperature of 90.degree.
- the monofilament was passed through a heating furnace to the third draw frame.
- the peripheral speed of the godets of the third stretching unit was also 198 m/min.
- the drawn monofilament was then wound onto a "K 160" type sleeve.
- the winder was operated at a speed of 195 m/min.
- the degree of stretching was 1:3.4.
- the diameter of the monofilament produced in this way is 300 ⁇ m.
- the characterization of the monofilament with regard to its physical textile properties showed a maximum elongation at break of 23%, a tensile strength of 62 mN/tex and an initial modulus of 1024 MPa.
- the electrical resistance of the monofilament as a function of temperature was measured using a four-prong device placed in an environmental chamber. The temperature was gradually increased from 24 °C (room temperature) to values of 30 °C, 40 °C, 50 °C, 60 °C, 70 °C and 80 °C. The measurement was carried out simultaneously on 8 sections of the monofilament with a measurement section or length of 75 mm each.
- a blend with a proportion of 34.3% by weight of polypropylene of the Moplen® 462 R type and low-density polyethylene (LDPE) of the type Lupolen® with a proportion of 30% by weight and as a conductivity additive was used as the matrix polymer or compound component A or compound component B with a proportion of 28.0% by weight of a conductive carbon black (carbon black) of the "Super Conductive Furnace N 294" type.
- Compound component C consisted of a blend of styrene block copolymer and poly(methyl methacrylate), each with a proportion of 1.125% by weight. 5.25% by weight of Rubitherm RT55 paraffin with a main melting peak at a temperature of 55° C.
- This PCM granulate, the matrix polymers polyethylene (LDPE Lupolen® ) in granulate form, polypropylene ( Moplen® 462 R) in granulate form and the compound component E were mixed together and placed in an extruder hopper.
- the conductive carbon black or the compound component B was placed in a metering device connected to the extruder.
- the dosing device enables the conductive carbon black to be introduced uniformly into the polymer melt.
- the extruder is a Haake Rheomex PTW 16/25 co-rotating twin screw extruder with a standard configuration, ie with segmented screws without return elements.
- the contents of the hopper and the conductive carbon black were plasticized, homogenized and extruded with the extruder.
- the hopper extruder and the dosing device were flooded with nitrogen.
- the screw speed was 180 rpm and the mass throughput was about 1 kg/h.
- the temperature of the extruder zones was as follows: 220°C at the feed, 240°C in zone 1, 260°C in zone 2, 240°C in zone 3 and 220°C at the strand die.
- the inside diameter of the strand die was 3 mm.
- the extruded and cooled polymer strand was granulated in a granulator.
- the granules obtained in this way had the following composition: - 34.3% by weight polypropylene as part of compound component A; - 30.0% by weight Low density polyethylene (LDPE) as part of compound component A; - 28.0% by weight conductive carbon black as compound component B; - 7.5% by weight PCM granules with 70% by weight of paraffin as compound component D and 15% by weight each of SEEPS and PMMA as parts of compound component C; - 0.2% by weight Additives as compound component E.
- LDPE Low density polyethylene
- the multifilament yarn was post-stretched using a three-stage stretching unit.
- the circumferential speed of the godets in the first stretching stage was 60 m/min and those in the second and third stretching stages were 192 m/min in each case.
- the multifilament was passed through a water-filled stretching bath at a temperature of 90.degree.
- the multifilament yarn was passed through a heating tunnel.
- the multifilament yarn was wound onto a "K 160" type tube.
- the winder was operated at a winding speed of 190 m/min.
- the degree of stretching of the multifilm yarn treated in this way with a fineness of 96 dtex f36 was 1:3.2.
- a maximum elongation at break of 192%, a tensile strength of 38 mN/tex and an initial modulus of 1190 MPa were measured on the non-postdrawn multifilament yarn with a fineness of 307 dtex f36.
- the diameter of the individual filaments of the multifilament yarn that was not post-drawn was 31 ⁇ m.
- the electrical resistance of the undrawn multifilament yarn as a function of temperature was measured using a four-point device placed in a climate chamber. The temperature was gradually increased from 24 °C (room temperature) to values of 30 °C, 40 °C, 50 °C, 60 °C, 70 °C and 80 °C. The measurement was carried out simultaneously on 8 sections of the multifilament yarn with a measurement section or length of 75 mm each.
- this multifilament yarn a polymer composition was selected which, due to the proportion and type of conductivity component B, led to relatively good specific electrical conductivity and from which stretchable multifilaments could nevertheless be produced.
- the electrical resistance of the multifilament yarn with a fineness of 307 dtex f36 at a temperature of 24 °C is lower by a factor of 4.6 compared to the monofilament with a fineness of 760 dtex (diameter 300 ⁇ m) in relation to the fineness or cross-sectional area.
- the multifilament yarn has a PTC intensity that largely corresponds to that of monofilaments.
- a blend with a proportion of 34.3% by weight of polypropylene of the Moplen® 462 R type and low-density polyethylene (LDPE) of the Lupolen® type with a proportion of 30% by weight as a conductivity additive was used as the matrix polymer or compound component A or compound component B with a proportion of 28.0% by weight of a conductive carbon black (carbon black) of the "Super Conductive Furnace N 294" type.
- Compound component C consisted of a blend of styrene block copolymer and poly(methyl methacrylate), each with a proportion of 1.125% by weight. 5.25% by weight of Rubitherm RT55 paraffin with a main melting peak at a temperature of 55° C.
- This PCM granulate, the matrix polymers polyethylene (LDPE Lupolen® ) in granulate form, polypropylene ( Moplen® 462 R) in granulate form and the compound component E were mixed together and placed in an extruder hopper.
- the conductive soot or the Compound component B was placed in a metering device connected to the extruder.
- the dosing device enables the conductive carbon black to be introduced uniformly into the polymer melt.
- the extruder is a Haake Rheomex PTW 16/25 co-rotating twin screw extruder with a standard configuration, ie with segmented screws without return elements.
- the contents of the hopper and the conductive carbon black were plasticized, homogenized and extruded with the extruder.
- the hopper extruder and the dosing device were flooded with nitrogen.
- the screw speed was 180 rpm and the mass throughput was about 1 kg/h.
- the temperature of the extruder zones was as follows: 220°C at the feed, 240°C in zone 1, 260°C in zone 2, 240°C in zone 3 and 220°C at the strand die.
- the inside diameter of the strand die was 3 mm.
- the extruded and cooled polymer strand was granulated in a granulator.
- the granules obtained in this way had the following composition: - 34.3% by weight polypropylene as part of compound component A; 30% by weight Low density polyethylene (LDPE) as part of compound component A; - 28.0% by weight conductive carbon black as compound component B; - 7.5% by weight PCM granules with 70% by weight of paraffin as compound component D and 15% by weight each of SEEPS and PMMA as parts of compound component C; - 0.2% by weight Additives as compound component E.
- LDPE Low density polyethylene
- the powder was placed in the extruder hopper under a nitrogen purge.
- the temperatures in the seven extruder zones were 190 °C in zone 1, 200 °C in zone 2, 210 °C in zones 3, 4, 5, 6 and 220 °C at the slot die.
- the film die had a slot width of 50 mm and a slot width of 300 ⁇ m.
- the single-screw extruder was operated at a screw speed of 8 revolutions per minute and a mass throughput of 3.5 g/min.
- the polymer melt or web emerging from the slot die was drawn off at a speed of 0.6 m/min via a chill roll and a downstream strip take-off device.
- the chill roll temperature was 36°C.
- foil webs with a width of 40 to 50 mm and a thickness of 160 to 240 ⁇ m could be produced continuously.
- the term “equivalent diameter” means the diameter of an "equivalent” spherical particle having the same chemical composition and surface section (electron microscope imaging) as the particle under study.
- the surface section of each (irregularly shaped) particle under investigation is assigned to a spherical particle with a diameter consistent with the measured signal.
- the distribution of carbon black agglomerates and aggregates in the moldings according to the invention is determined according to ASTM D 3849-14a.
- a volume of about 1 ml of the shaped body to be examined is first dissolved in a suitable solvent such as hexafluoroisopropanol, m-cresol, 2-chlorophenol, phenol, tetrachloroethane, dichloroacetic acid, dichloromethane or butanone.
- a suitable solvent such as hexafluoroisopropanol, m-cresol, 2-chlorophenol, phenol, tetrachloroethane, dichloroacetic acid, dichloromethane or butanone.
- the solution is prepared at elevated temperature and for a period of up to 24 hours.
- the resulting polymeric solution is ultrasonically dispersed or diluted in approximately 3 mL of chloroform and applied to sample grids for scanning transmission electron microscopy (RTEM) analysis.
- the RTEM generated images of the dilute polymeric solutions are analyzed using image analysis software such as ImageJ to determine the area or equivalent diameter of carbon black agglomerates and aggregates.
Description
Die vorliegende Erfindung betrifft elektrisch leitfähige Formkörper, wie im Anspruch 1 angegeben, aus einer elektrisch leitfähigen Polymerzusammensetzung mit inhärentem positivem Temperaturkoeffizienten (PTC), die mindestens ein organisches Matrixpolymer, submikro- oder nanoskalige, elektrisch leitfähige Partikel und mindestens ein Phasenwechselmaterial mit einer Phasenübergangstemperatur im Bereich von -42 °C bis + 150 °C enthält. Die Formkörper entstehen im Spritzgussverfahren und sind elektrisch leitfähige Monofilamente, Multifilamente, Fasern oder Vliese, die beispielsweise in Automobil-Sitzheizungen oder Heizdecken oder technischen Textilien eingesetzt werden können und den Stromfluss selbst regulieren.The present invention relates to electrically conductive moldings, as specified in
Sogenannte Kaltleiter, PTC-Widerstände oder PTC-Thermistoren, die einen positiven Temperaturkoeffizienten (PTC - positive temperature coefficient) des spezifischen elektrischen Widerstandes aufweisen, sind elektrisch leitfähige Materialien, die bei niedrigen Temperaturen den Strom besser leiten als bei höheren Temperaturen. Der spezifische elektrische Widerstand steigt mit der Temperatur in einem relativ eng begrenzten Temperaturbereich deutlich an. Solche Materialien können für Heizelemente, strombegrenzende Schalter oder Sensoren eingesetzt werden. Bekannte PTC-Polymerzusammensetzungen haben bezogen auf den Widerstand bei Raumtemperatur, d. h. bei etwa 24 °C einen niedrigen Leitungswiderstand, so dass Strom fließen kann. Bei sehr starker Temperaturerhöhung bis in die Nähe der Schmelztemperatur steigt der Widerstandswert auf das 104- bis 105-fache des bei Raumtemperatur (24 °C) gemessenen Wertes an.So-called PTC resistors or PTC thermistors, which have a positive temperature coefficient (PTC - positive temperature coefficient) of the specific electrical resistance, are electrically conductive materials that conduct electricity better at low temperatures than at higher temperatures. The specific electrical resistance increases significantly with temperature in a relatively narrowly limited temperature range. Such materials can be used for heating elements, current-limiting switches or sensors. Known PTC polymer compositions have a low line resistance based on the resistance at room temperature, ie at about 24° C., so that current can flow. If the temperature rises very sharply to near the melting point, the resistance value increases to 10 4 to 10 5 times the value measured at room temperature (24 °C).
Polymere PTC-Zusammensetzungen bestehen aus einer Mischung von organischen Polymeren insbesondere kristallinen und teilkristallinen Polymeren und elektrisch leitfähigen Additiven. Im Stand der Technik beruht der PTC-Effekt meist auf struktureller Veränderung kristalliner Polymerdomänen hin zu weniger kristalline bzw. amorphe Bereiche bei Temperaturerhöhung. Spezielle Polymermischungen umfassen neben den thermoplastischen Polymeren, thermoelastische Polymere, Harze und andere Elastomere. Ein Beispiel hierfür ist in
Derartige Polymerzusammensetzungen haben den Nachteil, dass der PTC-Effekt eingeschränkt ist auf ein Schaltverhalten, das auf struktureller Veränderung der als Hauptkomponente verwendeten Polymere beruht. Zudem ist die PTC-Intensität, d.h. die Widerstandsänderung sehr stark vom verwendeten Polymer bzw. Polymerblend abhängig.Such polymer compositions have the disadvantage that the PTC effect is limited to a switching behavior that is based on structural changes in the polymers used as the main component. In addition, the PTC intensity, ie the Change in resistance very much dependent on the polymer or polymer blend used.
Im Stand der Technik sind im Weiteren flüssige Polymerdispersionen mit PTC-Effekt bekannt, die für Beschichtungen oder Lackierungen vorgesehen sind. Bei diesen flüssigen Polymerdispersionen beruht der PTC-Effekt auf einem Additiv, wie Paraffin oder Polyethylenglykol (PEG), siehe z.B.
In der
Solche Imprägnierungs- und Beschichtungszusammensetzungen sind problematisch, da bei der Applikation Lösungsmittel häufig in unkontrollierter Weise ausgast, wobei sich in der Beschichtung mehr oder weniger sichtbare Krater und Blasen bilden. Bei unzureichender Vorbehandlung des zu beschichtenden Substrates, aufgrund zu kleiner oder zu großer Oberflächenenergie sowie ungeeigneter Oberflächenstruktur ist die Haftung der Beschichtung oft mangelhaft. Abplatzen und Abblättern der Funktionsschicht und damit verbunden eine erhebliche Beeinträchtigung der elektrischen Leitfähigkeit und des PTC-Effektes ist die Folge. Eine fehlerhafte Applikation der Imprägnierungs- bzw. Beschichtungszusammensetzung, unzureichende Trocknung und/oder Vernetzung, zu hohe Trocknungs- oder Aushärtungstemperaturen und -zeiten oder eine Überdosierung der Vernetzungsstrahlung beeinträchtigen unmittelbar die Haltbarkeit und Funktionalität der Beschichtung. Dies trifft insbesondere, aber nicht nur, auf die Beschichtung von Textilien zu. Zudem erfolgt oftmals partielles oder großflächiges "Ausbluten" von Paraffin aus derartigen Imprägnierungen und Beschichtungen, so dass diese nach kurzer Betriebsdauer versagen.Such impregnation and coating compositions are problematic since solvents frequently outgas in an uncontrolled manner during application, with more or less visible craters and bubbles forming in the coating. If the substrate to be coated is insufficiently pre-treated, the surface energy is too small or too large, and the surface structure is unsuitable, the adhesion of the coating is often poor. The result is flaking and flaking of the functional layer and, associated with this, a significant impairment of the electrical conductivity and the PTC effect. Incorrect application of the impregnation or coating composition, insufficient drying and/or crosslinking, drying or curing temperatures and times that are too high or an overdose of crosslinking radiation directly impair the durability and functionality of the coating. This applies in particular, but not only, to the coating of textiles. In addition, there is often partial or large-area "bleeding" of paraffin from such impregnations and coatings, so that these fail after a short period of operation.
Gegenstand des Artikels von
In der
In der
Die im Stand der Technik bekannten Materialien für die Herstellung von elektrisch leitfähigen Polymerformkörpern mit positivem Temperaturkoeffizient (PTC) basieren auf wässrigen Dispersionen und sind für Schmelzverfahren, wie Extrusion, Schmelzspinnen und Spritzguss ungeeignet. Zusammensetzungen für elektrisch leitfähige Polymerformkörper mit PTC im Sinne dieser Erfindung umfassen als wesentliche Bestandteile ein Matrixpolymer, ein Leitfähigkeitsadditiv und ein Phasenwechselmaterial. Die Verarbeitungstemperatur in Schmelzverfahren liegt üblicherweise im Bereich von 100 °C bis über 400 °C, insbesondere im Bereich von 105 °C bis 450 °C. Bei diesen Temperaturen ist das Phasenwechselmaterial flüssig und weist eine niedrige Viskosität auf. Demgegenüber weist das plastifizierte Matrixpolymer eine wesentlich höhere, z. T. um mehrere Größenordnungen höhere Viskosität auf. Auch bei guter Mischbarkeit von Matrixpolymer und Phasenwechselmaterial, wie z. B. im Fall von Polyethylen und Paraffin liegt das Phasenwechselmaterial als eine, im Matrixpolymer interkalierte Phase vor. Aufgrund der hohen mechanischen Belastung bzw. der hohen Scherspannung bzw. des Drucks an Extruder- oder Spritzgussdüsen in Verbindung mit der weit über dem Schmelzbereich des Phasenwechselmaterials liegenden Temperatur, wird das interkalierte niederviskose Phasenwechselmaterial aus dem Matrixpolymer verdrängt und teilweise an die Umgebung abgeführt. Zudem kann dieser Effekt in bestimmten Temperatur-Scherspannungs/Druck-Bereichen durch deformationsinduzierte Phasensegregation bzw. Entmischung verstärkt werden. Der Verlust an Phasenwechselmaterial ist besonders hoch, wenn der extrudierte Formkörper, wie beispielsweise eine Faser oder Folie in mindestens einer Raumrichtung eine geringe Abmessung von weniger als 1000 µm hat. Im Rahmen der vorliegenden Erfindung wird der Verlust an Phasenwechselmaterial auch mit dem Begriff "Ausbluten" bezeichnet.The materials known in the prior art for the production of electrically conductive polymer moldings with a positive temperature coefficient (PTC) are based on aqueous dispersions and are unsuitable for melting processes such as extrusion, melt spinning and injection molding. Compositions for electrically conductive polymer moldings with PTC within the meaning of this invention comprise a matrix polymer, a conductivity additive and a phase change material as essential components. The processing temperature in melt processes is usually in the range from 100°C to over 400°C, in particular in the range from 105°C to 450°C. At these temperatures, the phase change material liquid and has a low viscosity. In contrast, the plasticized matrix polymer has a much higher, z. T. higher viscosity by several orders of magnitude. Even with good miscibility of matrix polymer and phase change material such. in the case of polyethylene and paraffin, for example, the phase change material is present as a phase intercalated in the matrix polymer. Due to the high mechanical load or the high shear stress or the pressure at extruder or injection molding nozzles in connection with the temperature, which is well above the melting range of the phase change material, the intercalated low-viscosity phase change material is displaced from the matrix polymer and partially discharged into the environment. In addition, this effect can be intensified in certain temperature/shear stress/pressure ranges by deformation-induced phase segregation or demixing. The loss of phase change material is particularly high when the extruded shaped body, such as a fiber or film, has small dimensions of less than 1000 μm in at least one spatial direction. In the context of the present invention, the loss of phase change material is also referred to by the term “bleeding out”.
Im Weiteren wird das Phasenwechselmaterial beim vorgesehenen Gebrauch des PTC-Formkörpers erwärmt und verflüssigt, wobei der PTC-Formkörper z. T. erheblicher mechanischer Belastung ausgesetzt ist. Daher "blutet" auch beim Gebrauch des PTC-Formkörpers Phasenwechselmaterial aus.Furthermore, the phase change material is heated and liquefied during the intended use of the PTC molded body, the PTC molded body z. T. is exposed to considerable mechanical stress. Phase change material therefore "bleeds out" even when the PTC molded body is used.
Die Formkörper der vorliegenden Erfindung sind insbesondere für elektrisch heizbare Flächengebilde, wie Folien, Textilfasern und/oder Vliese vorgesehen. Die in einem stromdurchflossenen Leiter mit Widerstand R erzeugte Heizleistung P entspricht im Wesentlichen der sogenannten Ohm'schen Verlustleistung, die sich nach der Beziehung P=U·I=U2/R berechnet, wobei U die Spannung und I die Stromstärke bezeichnet. Je nach Anwendung und Größe des erfindungsgemäßen Formkörpers bzw. elektrisch heizbaren Flächengebildes ist eine Heizleistung P von einigen Watt bis zu etwa 2000 W zu erbringen. Die Heizleistung ist nach oben durch die verfügbare Spannung U und den Widerstand R des Formkörpers beschränkt. Die für stationäre oder portable Anwendungen, beispielweise im Haushalt, in einem Krankenhaus oder in einem Auto verfügbare Spannung liegt im Bereich von 1,5 bis 240 V. Bei vorgegebener Spannung U und gewünschter Heizleistung P berechnet sich der Widerstand R gemäß der Beziehung R = U2 /P. Für eine Heizleistung von beispielsweise P = 300 W bei einer Spannung U = 240 V beträgt der Widerstand R = (240 V)2 / 300 W = 192 Ω. Analog hierzu ist für eine Heizleistung P = 1 W bei einer Spannung U = 1 V ein Widerstand R = (1 V)2 / 1 W = 1 Ω erforderlich. Dementsprechend soll der elektrische Widerstand R des Formkörpers im Bereich von 1 bis 200 Ω liegen.The moldings of the present invention are intended in particular for electrically heatable sheetlike structures, such as foils, textile fibers and/or nonwovens. The heating power P generated in a current-carrying conductor with a resistance R essentially corresponds to the so-called ohmic power loss, which is calculated according to the relationship P=U·I=U 2 /R, where U denotes the voltage and I denotes the current intensity. Depending on the application and size of the shaped body according to the invention or electrically heatable sheetlike structure, a heating power P of a few watts up to about 2000 W is to be provided. The heating output is limited by the available voltage U and the resistance R of the shaped body. The voltage available for stationary or portable applications, for example in the home, in a hospital or in a car, is in the range of 1.5 to 240 V. With a given voltage U and the desired heating power P, the resistance R is calculated according to the relationship R = U 2 / p. For a heating power of, for example, P = 300 W at a voltage U = 240 V, the resistance is R = (240V) 2 / 300W = 192Ω. Analogous to this, a resistance R = (1 V) 2 / 1 W = 1 Ω is required for a heating power P = 1 W at a voltage U = 1 V. Accordingly, the electrical resistance R of the shaped body should be in the range from 1 to 200 Ω.
Der Widerstand R eines stromdurchflossenen Körpers hängt ab von der Länge L des von Strom durchflossenen Weges bzw. Pfades und von der Querschnittsfläche A des Körpers in einer zum Strompfad senkrechten Ebene gemäß der Beziehung R = ρ·L/A, worin ρ den spezifischen elektrischen Widerstand des Körpers in Einheiten von Ω·mm2 / m, oft jedoch von Ω·m oder Ω·cm bezeichnet. Der spezifische elektrische Widerstand ist eine von der Geometrie des Körpers unabhängige Materialkonstante. Zur Veranschaulichung sei eine Folie mit einer Dicke D = 200 µm, einer stromdurchflossenen Länge L = 1000 mm und einer Breite B = 800 mm betrachtet. Der Widerstand R der Folie über die stromdurchflossene Länge L betrage R = 100 Ω. Hieraus ergibt sich für den spezifischen Widerstand ρ des Folienmaterials ein Wert von:
Der spezifische Widerstand ρ eines leitfähigen Formkörpers ist bestimmt durch den Gehalt und die elektrische Leitfähigkeit des Leitfähigkeitsadditivs. Der für die vorstehend erörterten Heizanwendungen benötigte spezifische Widerstand kann prinzipiell durch einen entsprechend hohen Gehalt an Leitfähigkeitsadditiv realisiert werden. Allerdings stellen die damit verbundenen Kosten und/oder die Beeinträchtigung der mechanischen Eigenschaften des Formkörpers für viele Anwendungen ein erhebliches Hindernis dar.The specific resistance ρ of a conductive shaped body is determined by the content and the electrical conductivity of the conductivity additive. In principle, the specific resistance required for the heating applications discussed above can be achieved by means of a correspondingly high content of conductivity additive. However, the associated costs and/or the impairment of the mechanical properties of the molded body represent a significant obstacle for many applications.
Um dem erfindungsgemäßen Polymerformkörper eine vorgegebene elektrische Leitfähigkeit bzw. spezifischen elektrischen Widerstand zu verleihen, muss das Leitfähigkeitsadditiv in der Polymermatrix ein leitfähiges Netzwerk mit geeigneter Morphologie ausbilden. Zugleich darf der Anteil des Leitfähigkeitsadditivs einen bestimmten Wert nicht überschreiten, um die mechanischen Eigenschaften des Formkörpers, wie beispielsweise Bruchdehnung nicht zu stark zu beeinträchtigen.In order to impart a predetermined electrical conductivity or specific electrical resistance to the polymer molding according to the invention, the conductivity additive in the polymer matrix must form a conductive network with a suitable morphology. At the same time, the proportion of the conductivity additive must not exceed a specific value in order not to impair the mechanical properties of the shaped body, such as elongation at break, too severely.
Der vorliegenden Erfindung lag die Aufgabe zugrunde, die bisher bestehenden Probleme zu überwinden und eine Zusammensetzung bereitzustellen, aus der sich elektrisch leitfähige Formkörper mit einem inhärenten PTC-Effekt herstellen lassen. Die wasserfreie Zusammensetzung soll sich mit üblichen Schmelzverfahren, wie Extrusion, Schmelzspinnen oder Spritzguß zu Formkörpern verarbeiten lassen.The object of the present invention was to overcome the problems that existed up to now and to provide a composition from which electrically conductive shaped bodies with an inherent PTC effect can be produced. The anhydrous composition should be capable of being processed into shaped articles using conventional melting processes, such as extrusion, melt spinning or injection molding.
Dabei wurde gefunden, dass sich solche Formkörper in einem Schmelzverfahren herstellen lassen, wenn submikro- oder nanoskalige, elektrisch leitfähige Partikel zusammen mit einem Phasenwechselmaterial, das günstigerweise in Polymernetzwerkstrukturen eines Copolymers zu einem Masterbatch kombiniert wird sowie mit weiteren Compound-Komponenten eine thermoplastifizierbare Mischung bilden.It was found that such moldings can be produced in a melting process if submicro- or nanoscale, electrically conductive particles form a thermoplasticizable mixture together with a phase change material, which is advantageously combined in polymer network structures of a copolymer to form a masterbatch, and with other compound components.
Gelöst wird die Aufgabe demgemäß durch einen Formkörper aus einer elektrisch leitfähigen Zusammensetzung mit inhärentem positivem Temperaturkoeffizienten, die mindestens ein organisches Matrixpolymer (Compound-Komponente A), submikro- oder nanoskalige, elektrisch leitfähige Partikel (Compound-Komponente B) und mindestens ein Phasenwechselmaterial mit einer Phasenübergangstemperatur im Bereich von - 42 °C bis + 150 °C (Compound-Komponente D) sowie optional Stabilisatoren, Modifikatoren, Dispergiermittel und Verarbeitungshilfsmittel umfaßt, wobei die Polymerzusammensetzung einen Schmelzbereich im Intervall von 100 bis 450 °C aufweist, dadurch gekennzeichnet, dass das Phasenwechselmaterial in ein organisches Netzwerk aus mindestens einem Copolymer auf Basis von mindestes zwei verschiedenen ethylenisch ungesättigten Monomeren (Compound-Komponente C) eingebunden ist, sowie durch die Art und die Phasenübergangstemperatur des Phasenwechselmaterials die Einstellung des Temperaturbereichs für das Einsetzen der Wirkung des PTC-Effektes realisiert wird und der PTC-Effekt aus der Volumenvergrößerung des Phasenwechselmaterials in Folge der Temperaturerhöhung resultiert, die elektrisch leitfähigen Formköper bei Eintritt des PTC-Effektes keine Änderungen in der Morphologie der kristallinen Strukturen erfahren und nicht schmelzen. Die Gebrauchseigenschaften der elektrisch leitfähigen Formkörper sind nicht negativ beeinträchtigt. Eine Temperaturerhöhung um 60 °C führt dabei zu einer Erhöhung der PTC-Intensität um 50 % oder mehr. Bevorzugt führt eine solche Temperaturerhöhung zu einer Erhöhung der PCT-Intensität um mindestens 75 %, besonders bevorzugt um mindestens 100 %, wie auch in den nachfolgenden Beispielen gezeigt. Der Temperaturwechsel kann beliebig oft wiederholt werden, ohne dass sich dadurch die Morphologie in den kristallinen Bereichen des Formkörpers ändert.The object is accordingly achieved by a molded body made from an electrically conductive composition with an inherent positive temperature coefficient, which contains at least one organic matrix polymer (compound component A), submicroscale or nanoscale, electrically conductive particles (compound component B) and at least one phase change material with a Phase transition temperature in the range from - 42 °C to + 150 °C (compound component D) and optionally stabilizers, modifiers, dispersants and processing aids, the polymer composition having a melting range in the interval from 100 to 450 °C, characterized in that the Phase change material is integrated into an organic network of at least one copolymer based on at least two different ethylenically unsaturated monomers (compound component C), as well as the setting of the temperature range for d as the onset of the PTC effect is realized and the PTC effect results from the increase in volume of the phase change material as a result of the temperature increase, the electrically conductive molded bodies do not experience any changes in the morphology of the crystalline structures when the PTC effect occurs and do not melt. The performance properties of the electrically conductive moldings are not adversely affected. A temperature increase of 60 °C leads to an increase in the PTC intensity of 50% or more. Such a temperature increase preferably leads to an increase in the PCT intensity by at least 75%, particularly preferably by at least 100%, as also shown in the examples below. The temperature change can be repeated as often as desired without the morphology in the crystalline areas of the shaped body changing as a result.
Bei der Herstellung der elektrisch leitfähigen Zusammensetzung kann das Phasenwechselmaterial in reiner Form oder in Form eines Masterbatches mit den übrigen Komponenten vermischt werden.When producing the electrically conductive composition, the phase change material can be mixed with the other components in pure form or in the form of a masterbatch.
In einer bevorzugten Ausführungsform besteht die Zusammensetzung aus 10 bis 90 Gew.-% Matrixpolymer, 0,1 bis 30 Gew.-% an elektrisch leitfähigen Partikeln, 2 bis 50 Gew.-% Phasenwechselmaterial mit einer Phasenübergangstemperatur im Bereich von -42 °C bis 150 °C, 0 bis 10 Gew.-% Verarbeitungshilfsmitteln sowie Stabilisatoren, Modifikatoren und Dispergiermittel, bezogen auf das Gesamtgewicht der Zusammensetzung, wobei die Summe der Gewichtsanteile aller Bestandteile der Zusammensetzung 100 Gew.-% beträgt, und die Zusammensetzung einen Schmelzbereich im Intervall von 100 °C bis 450 °C hat.In a preferred embodiment, the composition consists of 10 to 90% by weight matrix polymer, 0.1 to 30% by weight of electrically conductive particles, 2 to 50% by weight Phase change material with a phase transition temperature in the range from -42 °C to 150 °C, 0 to 10% by weight of processing aids and stabilizers, modifiers and dispersing agents, based on the total weight of the composition, the sum of the parts by weight of all components of the composition being 100% by weight -% and the composition has a melting range in the
In bevorzugten Ausführungsformen
- ist die Zusammensetzung vernetzbar;
- hat das Matrixpolymer einen Schmelzbereich
im Intervall von 100 °C bis 450 °C; - hat das Matrixpolymer in Verbindung mit den Verarbeitungshilfsmitteln und/oder Stabilisatoren, Modifikatoren und Dispergiermitteln einen Schmelzbereich
im Intervall von 100 °C bis 450 °C; - liegt der Schmelzbereich des
Phasenwechselmaterials mindestens 10 °C,bevorzugt mindestens 20 °C, besonders bevorzugt mindestens 30 °C unterhalb des Schmelzbereiches des Matrixpolymers; - besteht das Matrixpolymer aus einem oder mehreren Polymeren, gewählt aus Ethylen-Homopolymeren, Ethylen-Copolymeren, Propylen-Homopolymeren, Propylen-Copolymeren, Homo- oder Copolyamiden, Homo- oder Copolyestern, Acrylat-Homo- oder -Copolymeren, Styrol-Homo- oder -Copolymeren, Polyvinylidenfluorid und Mischungen davon;
- enthält das Matrixpolymer kristalline, teilkristalline und/oder amorphe Polymere und mindestens ein Polymer aus der Gruppe der Polyethylene (PE), wie LDPE, LLDPE, HDPE und/oder der jeweiligen Copolymere, aus der Gruppe der ataktischen, syndiotaktischen und/oder isotaktischen Polypropylene (PP) und/oder der jeweiligen Copolymere, aus der Gruppe der Polyamide (PA), darunter insbesondere PA-11, PA-12, die PA-6.66-Copolymere, die PA-6.10-Copolymere, die PA-6.12-Copolymere, PA-6 oder PA-6.6, aus der Gruppe der Polyester (PES) mit aliphatischen, mit aliphatischen in Kombination mit cycloaliphatischen und/oder mit aliphatischen in Kombination mit aromatischen Bestandteilen, darunter insbesondere Polybutylenterephthalate (PBT), Polytrimethylenterephthalate (PTT) und Polyethylenterephthalate (PET) sowie der chemisch modifizierten Polyester, darunter insbesondere Glycol-modifizierte Polyethylenterephthalate (PET-G), aus der Gruppe der Polyvinylidenfluoride (PVDF) und der jeweiligen Copolymere, aus der Gruppe der vernetzbaren Copolymere sowie aus der Gruppe der Mischungen bzw. Blends dieser Polymere und/oder Copolymere entstammt;
- besteht das elektrisch leitfähige Material aus mikro- oder nanoskaligen Partikeln, Flocken, Nadeln, Röhren, Plättchen, Spheroiden oder Fasern aus Ruß, Graphit, expandiertem Graphit, Graphen, Metall, Metalllegierungen; aus elektrisch leitfähigen Polymeren; aus einwandigen oder mehrwandigen, offenen oder geschlossenen, leeren oder gefüllten Kohlenstoffnanoröhren (CNT); mit Metall gefüllten Kohlenstoffnanoröhren oder Mischungen der vorstehenden Materialien;
- besteht das elektrisch leitfähige Material aus einem Trägerpolymer und darin dispergierten mikro- oder nanoskaligen Partikeln, Flocken, Nadeln, Röhren, Plättchen, Spheroiden oder Fasern aus Ruß, Graphit, expandiertem Graphit, Graphen, Metall, Metalllegierungen; aus elektrisch leitfähigen Polymeren; aus einwandigen oder mehrwandigen, offenen oder geschlossenen, leeren oder gefüllten Kohlenstoffnanoröhren (CNT); mit Metall gefüllten Kohlenstoffnanoröhren und/oder Mischungen der vorstehenden Materialien.
- besteht das elektrisch leitfähige Material aus einem elektrisch leitfähigen Trägerpolymer und darin dispergierten mikro- oder nanoskaligen Partikeln, Flocken oder Fasern aus Ruß, Graphen, Metall, Metalllegierungen und/oder Kohlenstoffnanoröhren (CNT);
- enthält das elektrisch leitfähige Material mikro- oder nanoskalige Partikel, mikro- oder nanoskalige Fasern, mikro- oder nanoskalige Nadeln, mikro- oder nanoskalige Röhren, mikro- oder nanoskalige Plättchen, mikro- oder nanoskalige Spheroide oder Mischungen davon;
- enthält das elektrisch leitfähige Material Ruße des Typs Carbon Black, Leitruße, Graphite, expandierte Graphite, einwandige oder mehrwandige Kohlenstoffnanoröhren (CNT), offene oder geschlossene Kohlenstoffnanoröhren, leere oder metallisch gefüllte Kohlenstoffnanoröhren, Graphene, Kohlenstofffasern, Metallpartikel, insbesondere Metallplättchen der Metalle Ni, Ag, W, Mo, Au, Pt, Fe, Al, Cu, Ta, Zn, Co, Cr, Ti, Sn oder Legierungen davon;
- enthält das elektrisch leitfähige Material mit Silber dekorierte Kohlenstoffnanoröhren (CNT);
- weist das elektrisch leitfähige Material aus Ruß des Typs Carbon Black eine gemäß ASTM D 1510-16 bestimmte Jod-Adsorption von 400 bis 1800 mg/g auf;
- weist das elektrisch leitfähige Material aus Ruß des Typs Carbon Black eine gemäß ASTM D 2414-16 bestimmte Ölabsorption (Dibutylphthalat-Absorption) von 200 bis 500 cm3/100 g auf;
- besteht das elektrisch leitfähige Material aus Ruß des Typs Carbon Black und weist eine gemäß ASTM D 3493-16 bestimmte Ölabsorption (Dibutylphthalat-Absorption) nach vierfacher Kompression bei einem Druck von 165 MPa von 160 bis 240 cm3/100 g auf;
- besteht das elektrisch leitfähige Material aus Ruß des Typs Carbon Black und weist ein nach ASTM D 6086-09a
bestimmtes Leervolumen von 100 bis 250 cm3/100 g bei einem geometrisch gemittelten Druck PGM von 50 MPa auf, wobei PGM anhand des auf eine obere Stirnfläche einer zylindrischen Rußprobe ausgeübten Druckes P0 und des an einer unteren Stirnfläche der zylindrischen Rußprobe gemessenen Druckes P1 berechnet wird gemäß der Beziehung - besteht das elektrisch leitfähige Material aus Ruß des Typs Carbon Black, wobei die primären Rußpartikel einen gemäß ASTM D 3849-14a bestimmten mittleren äquivalenten Durchmesser
von 8bis 40 nm, 8bis 30 nm, 8bis 20nm oder 8 bis 16 nm aufweisen; - besteht das elektrisch leitfähige Material aus Ruß des Typs Carbon Black, wobei der Ruß Aggregate mit einem gemäß ASTM D 3849-14a bestimmten mittleren äquivalenten Durchmesser
von 100 bis 1000 nm, 100 bis 300 nm oder 100 bis 200 nm aufweist; - hat das Phasenwechselmaterial eine Phasenübergangstemperatur im Bereich von -42 °C bis 150 °C, - 42 °C bis 96 °C, 20
bis 80 °C, 20bis 60 °C, 20bis 50 °C, 30bis 80 °C, 30bis 60 °C oder 30bis 50 °C; - besteht das Phasenwechselmaterial aus einem oder mehreren Stoffen, bevorzugt aus niedermolekularen Kohlenwasserstoffen, die 10
bis 25 Kohlenstoffatome in einer Molekülkette aufweisen; niedermolekularen, nativen oder synthetischen, linearen oder verzweigten Polymeren; ionischen Flüssigkeiten; nativen oder synthetischen Paraffinen; nativen oder synthetischen Wachsen; nativen oder synthetischen Fettalkoholen; nativen oder synthetischen Wachsalkoholen; oder Mischungen von zwei oder mehr der genannten Materialien; - ist das Phasenwechselmaterial ein natürliches oder synthetisches Paraffin, ein Polyalkylenglykol (= Polyalkylenoxid), vorzugsweise Polyethylenglykol (= Polyethylenoxid), ein Polyesteralkohol, ein hochkristallines Polyethylenwachs oder eine Mischung davon;
- besteht das Phasenwechselmaterial aus einer oder mehreren ionischen Flüssigkeit(en);
- besteht das Phasenwechselmaterial aus einer Mischung einer oder mehrerer ionischer Flüssigkeiten mit einem oder mehreren Stoffen gewählt aus der Gruppe, umfassend natürliche und synthetische Paraffine, Polyalkylenglykole (= Polyalkylenoxide), vorzugsweise Polyethylenglykole (= Polyethylenoxide), Polyesteralkohole, hochkristalline Polyethylenwachse;
- enthält das Phasenwechselmaterial einen oder mehrere Stabilisatoren, gewählt aus funktionalisierten Polymeren, funktionalisierter mikro- oder nanoskaliger Kieselsäure, funktionalisierten mikro- oder nanoskaligen Schichtmineralien, n-octadecylaminfunktionalisierten Kohlenstoffnanoröhren und Mischungen davon;
- enthält das Phasenwechselmaterial ein oder mehrere Dispergiermittel, gewählt aus Ethylen-Vinylacetat-Copolymer, Polyethylen-poly(ethylen-propylen), Poly(ethylen-buten), Poly(maleinanhydrid amid co-α-olefin) und Mischungen davon;
- enthält das Phasenwechselmaterial einen Stabilisator und/oder ein Dispergiermittel, gewählt aus:
- Terblockpolymeren, wie Styrol-Butadien-Styrol (SBS) und Styrol-Isopren-Styrol (SIS);
- Tetrablockpolymeren, wie Styrol-Ethylen-Butylen-Styrol (SEBS), Styrol-Ethylen-Propylen-Styrol (SEPS), Styrol-poly(Isopren-Butadien)-Styrol (SIBS);
- Acrylnitril-Butadien-Styrol (ABS);
- Terblockpolymere, insbesondere Ethylen-Propylen-Dien (EPDM);
- Terpolymeren, insbesondere Ethylen-Vinylacetat-Vinylalkohol (EVAVOH);
- Ethylen-Maleinsäureanhydrid (EMSA), Ethylen-Acrylat-Maleinsäureanhydrid (EAMSA), Methylacrylat-Maleinsäureanhydrid, Ethylacrylat-Maleinsäureanhydrid, Propylacrylat-Maleinsäureanhydrid, Butylacrylat-Maleinsäureanhydrid;
- Ethylen-Glycidylmethacrylat (EGMA), Methyl-Glycidylmethacrylat, Ethyl-Glycidylmethacrylat, Propyl-Glycidylmethacrylat, Butyl-Glycidylmethacrylat;
- Ethylen-Acrylat-Glycidylmethacrylat (EAGMA), Methylacrylat-Glycidylmethacrylat, Ethylacrylat-Glycidylmethacrylat, Propylacrylat-Glycidylmethacrylat, Butylacrylat-Glycidylmethacrylat;
- Ethylen-Vinylacetat (EVA), Ethylen-Vinylalkohol (EVOH), Ethylen-Acrylsäureester (EAE), Ethylen-Methylacrylat (EMA), Ethylen-Ethylacrylat (EEA), Ethylen-Propylacrylat (EPA), Ethylen-Butylacrylat (EBA);
- Homo-, Co- und Pfropfcopolymeren des Polyethylens (PE), insbesondere LDPE, LLDPE, HDPE;
- Homo-, Co- und Pfropfcopolymeren des Propylens (PP), insbesondere ataktischen, syndiotaktischen und isotaktischen Polypropylenen;
- amorphen Polymeren wie Cycloolefin-Copolymeren (COC), Polymethylmethacrylat (PMMA), amorphem Polypropylen, amorphen Polyamiden, amorphen Polyestern oder Polycarbonaten (PC);
- liegt der Gewichtsanteil des
Matrixpolymers im Bereich 10bis 30 Gew.-%, 20bis 40 Gew.-%, 30bis 50 Gew.-%, 40bis 60 Gew.-%, 50bis 70 Gew.-%, 60bis 80 Gew.-% oder 70 bis 90 Gew.-% liegt, bezogen auf das Gesamtgewicht der Zusammensetzung, wobei die Summe der Gewichtsanteile aller einzelnen Bestandteile derZusammensetzung 100 Gew.-%; - liegt der Gewichtsanteil des elektrisch leitfähigen
0,1Materials im Bereich bis 4 Gew.-%, 2bis 6 Gew.-%, 4bis 8 Gew.-%, 6bis 10 Gew.-%, 8 bis 12 Gew.-%, 10 bis 14 Gew.-%, 12 bis 16 Gew.-%, 14 bis 18 Gew.-%, 16bis 20 Gew.-% , 18 bis 22 Gew.-%, 20bis 24 Gew.-%, 22 bis 26 Gew.-%, 24 bis 28 Gew.-% oder 26bis 30 Gew.-% , bezogen auf das Gesamtgewicht der Zusammensetzung, wobei die Summe der Gewichtsprozente aller einzelnen Bestandteile derZusammensetzung 100 Gew.-% beträgt; - besteht das elektrisch leitfähige Material aus Ruß des Typs Carbon Black und der Gewichtsanteil des elektrisch leitfähigen Additivs liegt im Bereich 18
bis 30 Gew.-%, 20bis 24 Gew.-%, 24 bis 28 Gew.-% oder 26bis 30 Gew.-% , bezogen auf das Gesamtgewicht der Zusammensetzung, wobei die Summe der Gewichtsprozente aller einzelnen Bestandteile derZusammensetzung 100 Gew.-% beträgt; - besteht das elektrisch leitfähige Material aus Kohlenstoffnanoröhren (CNT) und liegt der Gewichtsanteil des elektrisch leitfähigen
0,1Additivs im Bereich bis 4 Gew.-% , bezogen auf das Gesamtgewicht der Zusammensetzung, wobei die Summe der Gewichtsprozente aller einzelnen Bestandteile derZusammensetzung 100 Gew.-% beträgt; - besteht das elektrisch leitfähige Material aus Ruß (Carbon Black) und Kohlenstoffnanoröhren (CNT) besteht und liegt der Gewichtsanteil des elektrisch leitfähigen
0,1Additivs im Bereich bis 4 Gew.-% liegt, bezogen auf das Gesamtgewicht der Zusammensetzung, wobei die Summe der Gewichtsprozente aller einzelnen Bestandteile derZusammensetzung 100 Gew.-% beträgt; - liegt der Gewichtsanteil des
Phasenwechselmaterials im Bereich 2bis 6 Gew.-%, 4bis 8 Gew.-%, 6bis 10 Gew.-%, 8 bis 16 Gew.-%, 12bis 20 Gew.-%, 16bis 24 Gew.-%, 20 bis 28 Gew.-%, 24 bis 32 Gew.-%, 28 bis 36 Gew.-%, 32bis 40 Gew.-%, 36 bis 44 Gew.-%, 40 bis 48 Gew.-% oder 42bis 50 Gew.-% liegt, bezogen auf das Gesamtgewicht der Zusammensetzung, wobei die Summe aller Gewichtsprozente der einzelnen Bestandteile derZusammensetzung 100 Gew.-% beträgt;
und - enthält die Zusammensetzung optional ein oder mehrere Verarbeitungshilfsmittel und/oder Dispergiermittel und/oder Stabilisatoren und/oder Modifikatoren, die gewählt sind aus Gleitmitteln, epoxidiertem Sojaöl, thermischen Stabilisatoren, hochmolekularen Polymerisaten, Weichmachern, Antiblockmitteln, Farbstoffen, Farbpigmenten, Fungiziden, UV-Stabilisatoren, Brandschutzmitteln und Duftstoffen.
- the composition is crosslinkable;
- the matrix polymer has a melting range in the
interval 100°C to 450°C; - the matrix polymer in conjunction with the processing aids and/or stabilizers, modifiers and dispersants has a melting range in the
interval 100°C to 450°C; - the melting range of the phase change material is at least 10°C, preferably at least 20°C, more preferably at least 30°C below the melting range of the matrix polymer;
- the matrix polymer consists of one or more polymers selected from ethylene homopolymers, ethylene copolymers, propylene homopolymers, propylene copolymers, homo- or co-polyamides, homo- or co-polyesters, acrylate homo- or copolymers, styrene homo- or -copolymers, polyvinylidene fluoride and mixtures thereof;
- if the matrix polymer contains crystalline, partially crystalline and/or amorphous polymers and at least one polymer from the group of polyethylenes (PE), such as LDPE, LLDPE, HDPE and/or the respective copolymers, from the group of atactic, syndiotactic and/or isotactic polypropylenes ( PP) and/or the respective copolymers from the group of polyamides (PA), including in particular PA-11, PA-12, the PA-6.66 copolymers, the PA-6.10 copolymers, the PA-6.12 copolymers, PA -6 or PA-6.6, from the group of polyesters (PES) with aliphatic, with aliphatic in combination with cycloaliphatic and/or with aliphatic in combination with aromatic components, including in particular polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT) and polyethylene terephthalate (PET ) and chemically modified polyesters, including in particular glycol-modified polyethylene terephthalates (PET-G), from the group of polyvinylidene fluorides (PVDF) and the respective copolymers, from the group of crosslinkable copolymers and from the group of mixtures or blends of these polymers and/or copolymers;
- the electrically conductive material consists of micro- or nanoscale particles, flakes, needles, tubes, platelets, spheroids or fibers made of carbon black, graphite, expanded graphite, graphene, metal, metal alloys; from electrically conductive polymers; made of single-wall or multi-wall, open or closed, empty or filled carbon nanotubes (CNT); metal-filled carbon nanotubes or mixtures of the above materials;
- the electrically conductive material consists of a carrier polymer and micro- or nanoscale particles, flakes, needles, tubes, platelets, spheroids or fibers made of carbon black, graphite, expanded graphite, graphene, metal, metal alloys dispersed therein; from electrically conductive polymers; made of single-wall or multi-wall, open or closed, empty or filled carbon nanotubes (CNT); metal-filled carbon nanotubes and/or mixtures of the above materials.
- the electrically conductive material consists of an electrically conductive carrier polymer and microscale or nanoscale particles, flakes or fibers made of carbon black, graphene, metal, metal alloys and/or carbon nanotubes (CNT) dispersed therein;
- contains the electrically conductive material micro- or nano-scale particles, micro- or nano-scale fibers, micro- or nano-scale needles, micro- or nano-scale tubes, micro- or nano-scale platelets, micro- or nano-scale spheroids or mixtures thereof;
- contains the electrically conductive material soots of the carbon black type, conductive carbon blacks, graphite, expanded graphite, single-walled or multi-walled carbon nanotubes (CNT), open or closed carbon nanotubes, empty or metallically filled carbon nanotubes, graphene, carbon fibers, metal particles, in particular metal flakes of the metals Ni, Ag , W, Mo, Au, Pt, Fe, Al, Cu, Ta, Zn, Co, Cr, Ti, Sn or alloys thereof;
- the electrically conductive material contains carbon nanotubes (CNT) decorated with silver;
- the carbon black electrically conductive material has an iodine adsorption of 400 to 1800 mg/g as determined according to ASTM D 1510-16;
- the carbon black type carbon black electrically conductive material has an oil absorption (dibutyl phthalate absorption) of 200 to 500 cm 3 /100 g, determined according to ASTM D 2414-16;
- the electrically conductive material is carbon black type carbon black and has an oil absorption (dibutyl phthalate absorption) determined according to ASTM D 3493-16 after quadruple compression at a pressure of 165 MPa from 160 to 240 cm 3 /100 g;
- the electrically conductive material consists of soot of the carbon black type and has a void volume of 100 to 250 cm 3 /100 g, determined according to ASTM D 6086-09a, at a geometric mean pressure P GM of 50 MPa, where P GM is based on a pressure P 0 exerted on an upper end surface of a cylindrical soot sample and the pressure P 1 measured at a lower end surface of the cylindrical soot sample is calculated according to the relationship
- the electrically conductive material consists of carbon black type carbon black, the primary carbon black particles having a mean equivalent diameter of 8 to 40 nm, 8 to 30 nm, 8 to 20 nm or 8 to 16 nm as determined according to ASTM D 3849-14a;
- the electrically conductive material consists of carbon black type carbon black, the carbon black having aggregates with a mean equivalent diameter of 100 to 1000 nm, 100 to 300 nm or 100 to 200 nm, determined according to ASTM D 3849-14a;
- the phase change material has a phase transition temperature in the range of -42 °C to 150 °C, - 42 °C to 96 °C, 20 to 80 °C, 20 to 60 °C, 20 to 50 °C, 30 to 80 °C, 30 to 60°C or 30 to 50°C;
- the phase change material consists of one or more substances, preferably of low molecular weight hydrocarbons which have 10 to 25 carbon atoms in a molecular chain; low molecular weight, native or synthetic, linear or branched polymers; ionic liquids; native or synthetic paraffins; native or synthetic waxes; native or synthetic fatty alcohols; native or synthetic wax alcohols; or mixtures of two or more of the foregoing Materials;
- the phase change material is a natural or synthetic paraffin, a polyalkylene glycol (=polyalkylene oxide), preferably polyethylene glycol (=polyethylene oxide), a polyester alcohol, a highly crystalline polyethylene wax or a mixture thereof;
- the phase change material consists of one or more ionic liquids;
- the phase change material consists of a mixture of one or more ionic liquids with one or more substances selected from the group comprising natural and synthetic paraffins, polyalkylene glycols (=polyalkylene oxides), preferably polyethylene glycols (=polyethylene oxides), polyester alcohols, highly crystalline polyethylene waxes;
- the phase change material contains one or more stabilizers selected from functionalized polymers, functionalized micro- or nanoscale silica, functionalized micro- or nanoscale layered minerals, n-octadecylamine-functionalized carbon nanotubes, and mixtures thereof;
- the phase change material contains one or more dispersants selected from ethylene-vinyl acetate copolymer, polyethylene-poly(ethylene-propylene), poly(ethylene-butene), poly(maleic anhydride amide-co-α-olefin), and mixtures thereof;
- the phase change material contains a stabilizer and/or a dispersant selected from:
- terblock polymers such as styrene-butadiene-styrene (SBS) and styrene-isoprene-styrene (SIS);
- tetrablock polymers such as styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene (SEPS), styrene-poly(isoprene-butadiene)-styrene (SIBS);
- Acrylonitrile Butadiene Styrene (ABS);
- terblock polymers, especially ethylene-propylene-diene (EPDM);
- terpolymers, especially ethylene-vinyl acetate-vinyl alcohol (EVAVOH);
- Ethylene Maleic Anhydride (EMSA), Ethylene Acrylate Maleic Anhydride (EAMSA), Methyl Acrylate Maleic Anhydride, Ethyl Acrylate Maleic Anhydride, propyl acrylate maleic anhydride, butyl acrylate maleic anhydride;
- ethylene glycidyl methacrylate (EGMA), methyl glycidyl methacrylate, ethyl glycidyl methacrylate, propyl glycidyl methacrylate, butyl glycidyl methacrylate;
- ethylene acrylate glycidyl methacrylate (EAGMA), methyl acrylate glycidyl methacrylate, ethyl acrylate glycidyl methacrylate, propyl acrylate glycidyl methacrylate, butyl acrylate glycidyl methacrylate;
- ethylene vinyl acetate (EVA), ethylene vinyl alcohol (EVOH), ethylene acrylic acid ester (EAE), ethylene methyl acrylate (EMA), ethylene ethyl acrylate (EEA), ethylene propyl acrylate (EPA), ethylene butyl acrylate (EBA);
- homo-, co- and graft copolymers of polyethylene (PE), in particular LDPE, LLDPE, HDPE;
- homo-, co- and graft copolymers of propylene (PP), in particular atactic, syndiotactic and isotactic polypropylenes;
- amorphous polymers such as cycloolefin copolymers (COC), polymethyl methacrylate (PMMA), amorphous polypropylene, amorphous polyamides, amorphous polyesters or polycarbonates (PC);
- the proportion by weight of the matrix polymer is in the
range 10 to 30% by weight, 20 to 40% by weight, 30 to 50% by weight, 40 to 60% by weight, 50 to 70% by weight, 60 to 80 % by weight or 70 to 90% by weight, based on the total weight of the composition, the sum of the parts by weight of all the individual components of the composition being 100% by weight; - the proportion by weight of the electrically conductive material is in the range 0.1 to 4% by weight, 2 to 6% by weight, 4 to 8% by weight, 6 to 10% by weight, 8 to 12% by weight , 10 to 14% by weight, 12 to 16% by weight, 14 to 18% by weight, 16 to 20% by weight, 18 to 22% by weight, 20 to 24% by weight, 22 up to 26% by weight, 24 to 28% by weight or 26 to 30% by weight, based on the total weight of the composition, the sum of the weight percentages of all individual components of the composition being 100% by weight;
- the electrically conductive material consists of carbon black type carbon black and the weight fraction of the electrically conductive additive is in the range of 18 to 30% by weight, 20 to 24% by weight, 24 to 28% by weight or 26 to 30% by weight. -% based on the total weight the composition, wherein the sum of the weight percentages of all individual components of the composition is 100% by weight;
- the electrically conductive material consists of carbon nanotubes (CNT) and the proportion by weight of the electrically conductive additive is in the range from 0.1 to 4% by weight, based on the total weight of the composition, the sum of the weight percentages of all individual components of the composition being 100% by weight. -% amounts to;
- the electrically conductive material consists of carbon black and carbon nanotubes (CNT) and the weight fraction of the electrically conductive additive is in the range 0.1 to 4% by weight based on the total weight of the composition, the sum of the weight percentages of all individual components of the composition is 100% by weight;
- the weight fraction of the phase change material is in the
range 2 to 6 wt%, 4 to 8 wt%, 6 to 10 wt%, 8 to 16 wt%, 12 to 20 wt%, 16 to 24 wt% wt%, 20 to 28 wt%, 24 to 32 wt%, 28 to 36 wt%, 32 to 40 wt%, 36 to 44 wt%, 40 to 48 wt% -% or 42 to 50% by weight, based on the total weight of the composition, the sum of all weight percentages of the individual components of the composition being 100% by weight;
and - the composition optionally contains one or more processing aids and/or dispersants and/or stabilizers and/or modifiers selected from lubricants, epoxidized soybean oil, thermal stabilizers, high molecular weight polymers, plasticizers, antiblocking agents, dyes, color pigments, fungicides, UV stabilizers, fire retardants and fragrances.
Der erfindungsgemäße Formkörper ist ein Monofilament, Multifilament, eine Faser, oder ein Vlies. Monofilamente weisen vorzugsweise einen mittleren Durchmesser von 8 bis 400 µm, von 80 bis 300 µm, insbesondere von 100 bis 300 µm auf. Multifilamente bestehen zweckmäßig aus 8 bis 48 Einzelfilamenten. wobei die Einzelfilamente bevorzugt einen mittleren Durchmesser von 8 bis 40 µm aufweisen.The shaped body according to the invention is a monofilament, multifilament, fiber or fleece. Monofilaments preferably have an average diameter of 8 to 400 μm, 80 to 300 μm, in particular 100 to 300 μm. Multifilaments expediently consist of 8 to 48 individual filaments. the individual filaments preferably having an average diameter of 8 to 40 μm.
Weitere bevorzugte Ausführungsformen der Erfindung sind dadurch gekennzeichnet, dass der Formkörper
- Ruß des Typs Carbon Black enthält, wobei die primären Rußpartikel einen nach ASTM D 3849-14a an einer Lösung der Zusammensetzung bestimmten mittleren äquivalenten Durchmesser
von 8bis 40 nm, 8bis 30 nm, 8bis 20nm oder 8 bis 16 nm aufweisen; - Ruß des Typs Carbon Black enthält, wobei der Ruß Aggregate mit einem nach ASTM D 3849-14a an einer Lösung der Formkörper-Zusammensetzung bestimmten mittleren äquivalenten Durchmesser
von 100 bis 1000 nm, 100 bis 300 nm oder 100 bis 200 nm aufweist; - bei einer
Temperatur von 24 °C einen spezifischen elektrischen Widerstand ρ von 0,001 3,0 Ω·m,bis bevorzugt von 0,01 0,1 Ω·m, besonders bevorzugtbis von 0,01bis 0,09 Ω·m,speziell von 0,02bis 0,08 Ω·m odervon 0,03bis 0,08 Ω·m aufweist; - bei einer
Temperatur von 24 °C einen spezifischen elektrischen Widerstand ρvon 0,04bis 0,08 Ω·m, 0,06 0,1 Ω·m, 0,08bis bis 0,12 Ω·m, 0,1 0,3 Ω·m, 0,2bis 0,4 Ω·m, 0,3bis 0,5 Ω·m, 0,4bis 0,6 Ω·m, 0,3bis 0,5 Ω·m, 0,4bis 0,6 Ω·m, 0,5bis 0,7 Ω·m, 0,6bis 0,8 Ω·m, 0,7bis 0,9 Ω·m, 0,8bis 1,0 Ω·m, 1,0bis 2,0 Ω·bis 2,0m oder 3,0 Ω·m aufweist;bis im Temperaturbereich von 24 °C ≤ T ≤ 90 °C einen temperaturabhängigen spezifischen elektrischen Widerstand p(T) aufweist, wobei das Verhältnis p(T) / p(24 °C) mit zunehmenderTemperatur T von 1 auf einen 1,1Wert von bis 30, 1,1bevorzugt von bis 5, 1,1besonders bevorzugt von bis 4, 1,1speziell von bis 3, ansteigt;im Temperaturbereich von 24 °C ≤ T ≤ 90 °C einen temperaturabhängigen spezifischen elektrischen Widerstand p(T) aufweist, wobei das Verhältnis p(T) / p(24 °C) mit zunehmenderTemperatur T von 1 auf einenWert von 10 bis 21,bevorzugt von 1 auf einenWert von 15 bis 21, ansteigt;im Temperaturbereich von 24 °C ≤ T ≤ 90 °C einen temperaturabhängigen spezifischen elektrischen Widerstand p(T) aufweist, wobei das Verhältnis p(T) / p(24 °C) mit zunehmenderTemperatur T von 1 auf einen 1,1 bis 21 ansteigt und im Steigungsbereich der Mittelwert des Steigungsgradienten [ρ(T+ΔT) - p(T)] / [p(24 °C)·ΔT] zwischen 0,1 / °C und 3,5 / °C beträgt;Wert von im Temperaturbereich von 24 °C ≤ T ≤ 90 °C einen temperaturabhängigen spezifischen elektrischen Widerstand p(T) aufweist, wobei das Verhältnis p(T) / p(24 °C) mit zunehmenderTemperatur T von 1 auf einen 1,1 bis 21 ansteigt und im Steigungsbereich der Mittelwert des Steigungsgradienten [ρ(T+ΔT) - p(T)] / [p(24 °C)·ΔT] zwischen 0,1 / °C und 1,5 / °C beträgt;Wert von im Temperaturbereich von 24 °C ≤ T ≤ 90 °C einen temperaturabhängigen spezifischen elektrischen Widerstand p(T) aufweist, wobei das Verhältnis p(T) / p(24 °C) mit zunehmenderTemperatur T von 1 auf einen 1,1 bis 21 ansteigt und im Steigungsbereich der Mittelwert des Steigungsgradienten [ρ(T+ΔT) - p(T)] / [p(24 °C)·ΔT] zwischen 0,8 / °C und 1,2 / °C beträgt;Wert von - bei einer
Temperatur von 24 °C einer Höchstzugkraft von 11 N/mm2 bis 1100 N/mm2 standhält; - bei einer
Temperatur von 24 °Ceine Bruchdehnung von 5bis 60 %, 5bis 30 %, 5bis 20% oder 10bis 30 % aufweist; - bei einer
Temperatur von 24 °C einen Elastizitätsmodul von mindestens 110 N/mm2, bevorzugt jedoch von 1800 bis 3200 N/mm2 hat; und/oder - als Folie ausgebildet ist und bei einer
Temperatur von 24 °Ceine Schlagzugzähigkeit von 40bis 60 KJ/m2 aufweist.
- contains carbon black type carbon black, the primary carbon black particles having a mean equivalent diameter of 8 to 40 nm, 8 to 30 nm, 8 to 20 nm or 8 to 16 nm, determined according to ASTM D 3849-14a on a solution of the composition;
- contains carbon black type carbon black, the carbon black having aggregates with an average equivalent diameter of 100 to 1000 nm, 100 to 300 nm or 100 to 200 nm, determined according to ASTM D 3849-14a on a solution of the molding composition;
- at a temperature of 24° C., a specific electrical resistance ρ of from 0.001 to 3.0 Ω·m, preferably from 0.01 to 0.1 Ω·m, particularly preferably from 0.01 to 0.09 Ω·m, specifically from 0.02 to 0.08 Ω·m or from 0.03 to 0.08 Ω·m;
- at a temperature of 24 °C an electrical resistivity ρ of 0.04 to 0.08 Ω m, 0.06 to 0.1 Ω m, 0.08 to 0.12 Ω m, 0.1 to 0.3Ωm, 0.2 to 0.4Ωm, 0.3 to 0.5Ωm, 0.4 to 0.6Ωm, 0.3 to 0.5Ωm , 0.4 to 0.6 Ω m, 0.5 to 0.7 Ω m, 0.6 to 0.8 Ω m, 0.7 to 0.9 Ω m, 0.8 to 1 .0 Ω·m, 1.0 to 2.0 Ω·m or 2.0 to 3.0 Ω·m;
- has a temperature-dependent specific electrical resistance p(T) in the temperature range of 24 °C ≤ T ≤ 90 °C, with the ratio p(T) / p(24 °C) increasing from 1 to a value of 1.1 with increasing temperature T to 30, preferably from 1.1 to 5, more preferably from 1.1 to 4, especially from 1.1 to 3;
- has a temperature-dependent specific electrical resistance p(T) in the temperature range of 24 °C ≤ T ≤ 90 °C, with the ratio p(T) / p(24 °C) increasing from 1 to a value of 10 to 21 as the temperature T increases , preferably from 1 to a value of 15 to 21;
- has a temperature-dependent specific electrical resistance p(T) in the temperature range of 24 °C ≤ T ≤ 90 °C, with the ratio p(T) / p(24 °C) increasing from 1 to a value of 1.1 with increasing temperature T to 21 and in the gradient range the mean value of the gradient [ρ(T+ΔT) - p(T)] / [p(24 °C) ΔT] is between 0.1 / °C and 3.5 / °C;
- has a temperature-dependent specific electrical resistance p(T) in the temperature range of 24 °C ≤ T ≤ 90 °C, with the ratio p(T) / p(24 °C) increasing from 1 to a value of 1.1 with increasing temperature T to 21 and in the gradient range the mean value of the gradient [ρ(T+ΔT) - p(T)] / [p(24 °C) · ΔT] is between 0.1 / °C and 1.5 / °C;
- has a temperature-dependent specific electrical resistance p(T) in the temperature range of 24 °C ≤ T ≤ 90 °C, with the ratio p(T) / p(24 °C) increasing from 1 to a value of 1.1 with increasing temperature T to 21 and in the gradient range the mean value of the gradient [ρ(T+ΔT) - p(T)] / [p(24 °C) ΔT] is between 0.8 / °C and 1.2 / °C;
- withstands a maximum tensile force of 11 N/mm 2 to 1100 N/mm 2 at a temperature of 24 °C;
- has an elongation at break of 5 to 60%, 5 to 30%, 5 to 20% or 10 to 30% at a temperature of 24°C;
- at a temperature of 24°C, has a modulus of elasticity of at least 110 N/mm 2 , but preferably from 1800 to 3200 N/mm 2 ; and or
- is formed as a film and has an impact strength of 40 to 60 KJ/m 2 at a temperature of 24 °C.
In einer zweckmäßigen Ausgestaltung weist der erfindungsgemäße Formkörper bei einer Temperatur (T) oberhalb der Phasenübergangstemperatur des Phasenwechselmaterials einen spezifischen elektrischen Widerstand p(T) auf, der das 1,1 bis 30 fache, bevorzugt das 1,5 bis 21 fache, besonders bevorzugt das 3 bis 10 fache des spezifischen elektrischen Widerstands bei einer Temperatur unterhalb der Phasenübergangstemperatur beträgt.In an expedient embodiment, the shaped body according to the invention has a specific electrical resistance p(T) at a temperature (T) above the phase transition temperature of the phase change material which is 1.1 to 30 times, preferably 1.5 to 21 times, particularly preferably that 3 to 10 times the electrical resistivity at a temperature below the phase transition temperature.
Eine weitere Aufgabe der Erfindung besteht darin, elektrisch beheizbare Textilien bereitzustellen. Diese Aufgabe wird gelöst durch ein Textil, das Monofilamente, Multifilamente,Another object of the invention is to provide electrically heatable textiles. This problem is solved by a textile that contains monofilaments, multifilaments,
Fasern, oder Vlies aus der vorstehend beschriebenen Zusammensetzung enthält.Fibers, or fleece of the composition described above contains.
Im Rahmen der vorliegenden Erfindung bezeichnet der Begriff "Phasenwechselmaterial" einen einzelnen Stoff wie auch eine Zusammensetzung aus zwei oder mehr Stoffen, wobei der einzelne Stoff oder mindestens ein Stoff der Zusammensetzung eine Phasenübergangstemperatur in einem Bereich von -42 °C bis +150 °C aufweist. Der Phasenübergang ist vorzugsweise ein Übergang von fest zu flüssig, d.h. das Phasenwechselmaterial weist vorzugsweise einen Hauptschmelzpeak im Bereich von - 42 °C bis + 150 °C auf. Das Phasenwechselmaterial besteht beispielsweise aus einem Paraffin oder einer Zusammensetzung, die ein Paraffin und ein oder mehrere Polymere umfasst, wobei die Polymere das Paraffin binden und stabilisieren.In the context of the present invention, the term "phase change material" denotes a single substance as well as a composition of two or more substances, wherein the individual substance or at least one substance of the composition has a phase transition temperature in a range from -42 °C to +150 °C . The phase transition is preferably a solid-to-liquid transition, i.e. the phase change material preferably has a major melting peak in the range of -42°C to +150°C. The phase change material consists, for example, of a paraffin or a composition comprising a paraffin and one or more polymers, the polymers binding and stabilizing the paraffin.
Die Begriffe "submikroskalig" und "nanoskalig" bezeichnen Partikel und Körper, die in mindestens einer Raumrichtung eine Abmessung von weniger als 1000 nm, respektive von 100 nm oder weniger haben. Dementsprechend werden Partikel oder Plättchen, die in einer Raumrichtung beispielsweise eine Abmessung von 300 bis 800 nm aufweisen, als "mikroskalig" bezeichnet. Demgegenüber werden Partikel oder Fasern, die beispielsweise in einer Raumrichtung eine Abmessung von 10 bis 50 nm haben, als "nanoskalig" bezeichnet. Die Zusammensetzung enthält mindestens ein thermoplastisches organisches Polymer oder vernetzbares Copolymer, einen leitfähigen Füllstoff und Phasenwechselmaterialien sowie weitere inerte oder funktionelle Materialien. Die Auswahl der Materialkombination wird für den gewünschten Anwendungsfall zielgerichtet zusammengestellt. Zur Einstellung des PTC-Schaltverhaltens bei verschiedenen Übergangstemperaturen werden geeignete Phasenwechselmaterialien ausgewählt. Diese Materialien werden bevorzugt vor der Verwendung im Matrixpolymer oder im Matrixpolymerblend selbst in polymere Netzwerkstrukturen eingebracht und/oder können durch Additive in ihrem Viskositätsverhalten beeinflusst werden. Diese derart modifizierten Phasenwechselmaterialen werden im Matrixpolymer oder dem Matrixpolymerblend gemeinsam mit den leitfähigen Additiven intensiv eingemischt, so dass sich eine weitgehend homogene Verteilung der Leitfähigkeitsadditive und der Phasenwechselmaterialien ergibt. Die Polymerzusammensetzung weist dann einen PTC-Effekt auf. Zusätzlich können der erfindungsgemäßen Zusammensetzung weitere inerte oder funktionelle Additive zugegeben werden, wie beispielsweise Thermo- und/oder UV- Stabilisatoren, Oxidationsinhibitoren, Haftvermittler, Farbstoffe und Pigmente, Vernetzungsmittel, Prozesshilfsmittel und/oder Dispergierhilfsmittel. Ebenso können sonstige Mittel und Füllstoffe, insbesondere Siliciumcarbid, Bornitrid und/oder Aluminiumnitrid zur Erhöhung der Wärme- bzw. Temperaturleitfähigkeit zugefügt werden.The terms “submicroscale” and “nanoscale” refer to particles and bodies which have a dimension of less than 1000 nm or 100 nm or less in at least one spatial direction. Accordingly, particles or flakes which have a dimension of 300 to 800 nm in a spatial direction, for example, are referred to as “microscale”. In contrast, particles or fibers which, for example, have a dimension of 10 to 50 nm in one spatial direction are referred to as “nanoscale”. The composition contains at least one thermoplastic organic polymer or crosslinkable copolymer, a conductive filler, and phase change materials, as well as other inert or functional materials. The material combination is selected specifically for the desired application. Suitable phase change materials are selected to adjust the PTC switching behavior at different transition temperatures. These materials are preferably introduced into polymeric network structures before use in the matrix polymer or in the matrix polymer blend itself and/or their viscosity behavior can be influenced by additives. These phase change materials modified in this way are intensively mixed into the matrix polymer or the matrix polymer blend together with the conductive additives, resulting in a largely homogeneous distribution of the conductivity additives and the phase change materials. The polymer composition then has a PTC effect. In addition, other inert or functional additives can be added to the composition according to the invention, such as for example thermal and/or UV stabilizers, oxidation inhibitors, adhesion promoters, dyes and pigments, crosslinking agents, processing aids and/or dispersing aids. Other agents and fillers, in particular silicon carbide, boron nitride and/or aluminum nitride, can also be added to increase thermal conductivity.
Das Matrixpolymer bzw. der Matrixpolymerblend - nachfolgend als Compoundkomponente A bezeichnet - enthält ein oder mehrere kristalline, teilkristalline und/oder amorphe Polymere aus der Gruppe der Polyethylene (PE) wie LDPE, LLDPE, HDPE und/oder der jeweiligen Copolymere, aus der Gruppe der ataktischen, syndiotaktischen und/oder isotaktischen Polypropylene (PP) und/oder der jeweiligen Copolymere, aus der Gruppe der Polyamide (PA), darunter insbesondere PA-11, PA-12, die PA-6.66-Copolymere, die PA-6.10-Copolymere, die PA-6.12-Copolymere, PA-6 oder PA-6.6, aus der Gruppe der Polyester (PES) mit aliphatischen, mit aliphatischen in Kombination mit cycloaliphatischen und/oder mit aliphatischen in Kombination mit aromatischen Bestandteilen, darunter insbesondere Polybutylenterephthalate (PBT), Polytrimethylenterephthalate (PTT) und Polyethylenterephthalate (PET) sowie der chemisch modifizierten Polyester, darunter insbesondere Glykol-modifizierte Polyethylenterephthalate (PET-G), aus der Gruppe der Polyvinylidenfluoride (PVDF) und der jeweiligen Copolymere, aus der Gruppe der vernetzbaren Copolymere sowie aus der Gruppe der Mischungen bzw. Blends dieser Polymere und/oder Copolymere entstammt.The matrix polymer or the matrix polymer blend - hereinafter referred to as compound component A - contains one or more crystalline, semi-crystalline and/or amorphous polymers from the group of polyethylenes (PE) such as LDPE, LLDPE, HDPE and/or the respective copolymers from the group of atactic, syndiotactic and/or isotactic polypropylenes (PP) and/or the respective copolymers from the group of polyamides (PA), including in particular PA-11, PA-12, the PA-6.66 copolymers, the PA-6.10 copolymers , the PA-6.12 copolymers, PA-6 or PA-6.6, from the group of polyesters (PES) with aliphatic, with aliphatic in combination with cycloaliphatic and/or with aliphatic in combination with aromatic components, including in particular polybutylene terephthalate (PBT) , polytrimethylene terephthalate (PTT) and polyethylene terephthalate (PET) and chemically modified polyesters, including in particular glycol-modified polyethylene terephthalate (PET-G), from Group ppe of polyvinylidene fluoride (PVDF) and the respective copolymers, from the group of crosslinkable copolymers and from the group of mixtures or blends of these polymers and / or copolymers originates.
Das in der Zusammensetzung enthaltene Leitfähigkeitsadditiv (Compound-Komponente B) liegt in Form von mikro- oder nanoskaligen Domänen, mikro- oder nanoskaligen Partikeln, mikro- oder nanoskaligen Fasern, mikro- oder nanoskaligen Nadeln, mikro- oder nanoskaligen Röhrchen und/oder mikro- oder nanoskaligen Plättchen vor und besteht aus einem oder mehreren leitfähigen Polymeren, Ruß (Carbon Black), Leitruß, Graphit, expandiertem Graphit, einwandigen und/oder mehrwandigen Kohlenstoff-Nanoröhren (CNT), offenen und/oder geschlossenen Kohlenstoff-Nanoröhren, leeren und/oder mit einem Metall, wie Silber, Kupfer oder Gold gefüllten Kohlenstoff-Nanoröhren, Graphen, Kohlenstofffasern (CF), Flocken und/oder Partikeln aus einem Metall, wie Ni, Ag, W, Mo, Au, Pt, Fe, Al, Cu, Ta, Zn, Co, Cr, Ti, Sn oder Legierungen von zwei oder mehr Metallen. Gegebenenfalls umfasst das Leitfähigkeitsadditiv bzw. die Compoundkomponente B zudem ein Polymer, in dem die leitfähigen Partikel dispergiert sind, so dass die Compound-Komponente B bei der Herstellung von Formkörpern als Masterbatch eingesetzt werden kann. Gemäß der Erfindung ist ein Phasenwechselmaterial (Compound-Komponente D) in ein polymeres Netzwerk aus einer Compound-Komponente C eingebunden. Die Compound-Komponente C enthält ein oder mehrere Polymere aus der Gruppe der Terblockpolymere bestehend aus Styrol-Butadien-Styrol (SBS), aus Styrol-Isopren-Styrol (SIS), der Tetrablockpolymere bestehend aus Styrol-Ethylen-Butylen-Styrol (SEBS), aus Styrol-Ethylen-Propylen-Styrol (SEPS), aus Styrol-poly(Isopren-Butadien)-Styrol (SIBS), der Terblockpolymere bestehend aus Ethylen-Propylen-Dien (EPDM), der Terpolymere bestehend aus Ethylen, Vinylacetat und Vinylalkohol (EVAVOH), aus Ethylen, Methyl- und/oder Ethyl- und/oder Propyl- und/oder Butylacrylat und Maleinsäureanhydrid (EAEMSA), aus Etylen, Methyl- und/oder Ethyl- und/oder Propyl- und/oder Butylacrylat und Glycidylmethacrylat (EAEGMA), aus Acrylonitril, Butadien und Styrol (ABS), der Copolymere bestehend aus Ethylen und Maleinsäureanhydrid (EMSA), aus Ethylen und Glycidylmethacrylat (EGMA), aus Etylen und Vinylacetat (EVA), aus Ethylen und Vinylalkohol (EVOH), aus Ethylen und Acrylsäureester (EAE), wie Methyl- (EMA) und/oder Ethyl- (EEA) und/oder Propyl- (EPA) und/oder Butylacrylat (EBA) sowie und/oder aus der Gruppe der verschiedenartigen Polyethylene (PE) wie LDPE, LLDPE, HDPE und/oder der jeweiligen Copolymere, einschließlich der Pfropfcopolymere des Polyethylens, aus der Gruppe der ataktischen, syndiotaktischen und/oder isotaktischen Polypropylene (PP) und/oder der jeweiligen Copolymere, einschließlich der Pfropfcopolymere des Polypropylens entstammen. Der Begriff "Copolymer" schließt dabei auch Terpolymere sowie Polymere mit Einheiten aus 4 oder mehr verschiedenen Monomeren ein.The conductivity additive contained in the composition (compound component B) is in the form of microscale or nanoscale domains, microscale or nanoscale particles, microscale or nanoscale fibers, microscale or nanoscale needles, microscale or nanoscale tubes and/or microscale or nanoscale platelets and consists of one or more conductive polymers, carbon black, conductive carbon black, graphite, expanded graphite, single-walled and/or multi-walled carbon nanotubes (CNT), open and/or closed carbon nanotubes, empty and/or or carbon nanotubes, graphene, carbon fibers (CF), flakes and/or particles of a metal such as Ni, Ag, W, Mo, Au, Pt, Fe, Al, Cu filled with a metal such as silver, copper or gold , Ta, Zn, Co, Cr, Ti, Sn or alloys of two or more metals. Optionally, the conductivity additive or the compound component B also includes a polymer in which the conductive particles are dispersed, so that the compound component B in the Production of moldings can be used as a masterbatch. According to the invention, a phase change material (compound component D) is bound into a polymeric network of a compound component C. Compound component C contains one or more polymers from the group of terblock polymers consisting of styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), tetra-block polymers consisting of styrene-ethylene-butylene-styrene (SEBS) , from styrene-ethylene-propylene-styrene (SEPS), from styrene-poly(isoprene-butadiene)-styrene (SIBS), from terblock polymers consisting of ethylene-propylene-diene (EPDM), from terpolymers consisting of ethylene, vinyl acetate and vinyl alcohol (EVAVOH), from ethylene, methyl and/or ethyl and/or propyl and/or butyl acrylate and maleic anhydride (EAEMSA), from ethylene, methyl and/or ethyl and/or propyl and/or butyl acrylate and glycidyl methacrylate (EAEGMA), from acrylonitrile, butadiene and styrene (ABS), from the copolymers consisting of ethylene and maleic anhydride (EMSA), from ethylene and glycidyl methacrylate (EGMA), from ethylene and vinyl acetate (EVA), from ethylene and vinyl alcohol (EVOH). Ethylene and acrylic acid esters (EAE) such as methyl (EMA) and/or eth yl (EEA) and/or propyl (EPA) and/or butyl acrylate (EBA) and/or from the group of various polyethylenes (PE) such as LDPE, LLDPE, HDPE and/or the respective copolymers, including the graft copolymers of Polyethylene, from the group of atactic, syndiotactic and / or isotactic polypropylenes (PP) and / or the respective copolymers, including the graft copolymers of polypropylene originate. The term “copolymer” also includes terpolymers and polymers with units made up of 4 or more different monomers.
In einer bevorzugten Ausführungsform der Erfindung wird ein Masterbatch eingesetzt, welches das Leitfähigkeitsadditiv (Compound-Komponente B) und das Phasenwechselmaterial (Compound-Komponente D) dispergiert in der Compound-Komponente C enthält. Zweckmäßig wird der Zusammensetzung ein polymerer Modifikator hinzugefügt, der die thermoplastischen Eigenschaften und die Verarbeitbarkeit verbessert. Der polymere Modifikator ist vorzugsweise gewählt aus der Gruppe, umfassend amorphe Polymere wie Cycloolefin-Copolymere (COC), amorphes Polypropylen, amorphe Polyamide, amorphe Polyester oder Polycarbonate (PC).In a preferred embodiment of the invention, a masterbatch is used which contains the conductivity additive (compound component B) and the phase change material (compound component D) dispersed in the compound component C. A polymeric modifier is expediently added to the composition, which improves the thermoplastic properties and the processability. The polymeric modifier is preferably selected from the group comprising amorphous polymers such as cycloolefin copolymers (COC), amorphous polypropylene, amorphous polyamides, amorphous polyesters or polycarbonates (PC).
In einer weiteren Ausführungsform der Erfindung wird dem Phasenwechselmaterial oder der Compoundkomponente C ein mikro- oder nanoskaliger Stabilisator beigemengt.In a further embodiment of the invention, the phase change material or the Compound component C added a micro- or nanoscale stabilizer.
Erfindungsgemäß umfasst der Begriff "nanoskalige Materialien" Additive, die in Form eines Pulvers, einer Dispersion oder eines Polymerkomposits vorliegen und Partikel enthalten, die in mindestens einer Dimension, insbesondere der Dicke oder des Durchmessers eine Abmessung von kleiner 100 Nanometer aufweisen. So kommen als nanoskaliger Stabilisator vorzugsweise lipophile, hydrophobierte Schichtmineralien, z. B. lipophile Schichtsilikate, darunter lipophile Bentonite in Betracht, die in Plastifizierungs- und Mischprozessen bei der Verarbeitung des erfindungsgemäßen Zusammensetzung exfolieren. Diese exfolierten Partikel haben allgemein eine Länge und Breite von etwa 200 nm bis 1.000 nm und eine Dicke von etwa 1 nm bis 4 nm. Das Verhältnis von Länge und Breite zu Dicke (aspect ratio) beträgt vorzugsweise etwa 150 bis 1.000, bevorzugt 200 bis 500. Weitere bevorzugt zum Einsatz kommende hydrophobe viskositätssteigernde Mittel sind hydrophobierte nanoskalige pyrogene Kieselsäuren. Diese nanoskaligen pyrogenen Kieselsäuren bestehen allgemein aus Partikeln mit einem mittleren Durchmesser bevorzugt von 30 nm bis 100 nm.According to the invention, the term “nanoscale materials” includes additives that are in the form of a powder, a dispersion or a polymer composite and contain particles that are less than 100 nanometers in at least one dimension, in particular the thickness or diameter. Thus, preferably lipophilic, hydrophobic layered minerals, e.g. B. lipophilic phyllosilicates, including lipophilic bentonites, which exfoliate in plasticizing and mixing processes during processing of the composition according to the invention. These exfoliated particles generally have a length and width of about 200 nm to 1000 nm and a thickness of about 1 nm to 4 nm. The ratio of length and width to thickness (aspect ratio) is preferably about 150 to 1000, preferably 200 to 500 Further hydrophobic viscosity-increasing agents that are preferably used are hydrophobicized nanoscale pyrogenic silicas. These nanoscale fumed silicas generally consist of particles with an average diameter of preferably 30 nm to 100 nm.
In einer weiteren vorteilhaften Ausführungsform der Erfindung wird zur Anpassung der Schmelzeviskosität ein Gleitmittel eingesetzt. Das Gleitmittel kann dem Phasenwechselmaterial oder der Compoundkomponente C hinzugefügt werden.In a further advantageous embodiment of the invention, a lubricant is used to adjust the melt viscosity. The lubricant can be added to the phase change material or to compound component C.
Die erfindungsgemäße Zusammensetzung enthält ein Phasenwechselmaterial (phase change material bzw. PCM), vorliegend auch als Compound-Komponente D bezeichnet. Das Phasenwechselmaterial (Compound-Komponente D), hat eine Phasenübergangstemperatur im Bereich von -42 °C bis +150 °C, insbesondere von -30 °C bis +96 °C, bei der sich ihr Volumen bzw. ihre Dichte reversibel ändert. Das Phasenwechselmaterial bzw. die Compoundkomponente D ist gewählt aus der Gruppe umfassend natürliche und synthetische Paraffine, Polyalkylenglycole (= Polyalkylenoxide), vorzugsweise Polyethylenglykole (= Polyethylenoxide), Polyesteralkohole, hochkristalline Polyethylenwachse sowie Mischungen davon und/oder das Phasenwechselmaterial ist gewählt aus der Gruppe umfassend ionische Flüssigkeiten sowie Mischungen davon und/oder das Phasenwechselmaterial ist gewählt aus der Gruppe umfassend Mischungen aus natürlichen und synthetischen Paraffinen, Polyalkylenglykolen (= Polyalkylenoxiden), vorzugsweise Polyethylenglykolen (= Polyethylenoxiden), Polyesteralkoholen, hochkristallinen Polyethylenwachsen einerseits sowie ionischen Flüssigkeiten andererseits.The composition according to the invention contains a phase change material (phase change material or PCM), also referred to as compound component D here. The phase change material (compound component D) has a phase transition temperature in the range from -42° C. to +150° C., in particular from -30° C. to +96° C., at which its volume or its density changes reversibly. The phase change material or the compound component D is selected from the group consisting of natural and synthetic paraffins, polyalkylene glycols (=polyalkylene oxides), preferably polyethylene glycols (=polyethylene oxides), polyester alcohols, highly crystalline polyethylene waxes and mixtures thereof and/or the phase change material is selected from the group consisting of ionic ones Liquids and mixtures thereof and/or the phase change material is selected from the group comprising mixtures of natural and synthetic paraffins, polyalkylene glycols (=polyalkylene oxides), preferably polyethylene glycols (=polyethylene oxides), polyester alcohols, highly crystalline polyethylene waxes on the one hand and ionic liquids on the other.
Phasenwechselmaterial im Sinne dieser Erfindung sind alle Materialien, ausgewählt aus den im vorstehenden Absatz genannten Gruppen, die eine Phasenübergangstemperatur im Bereich von -42 °C bis +150 °C, insbesondere von -30 °C bis +96 °C haben, bei der sich ihr Volumen bzw. ihre Dichte reversibel ändert. Dabei können diese Phasenwechselmaterialien allein (in Rohform), verwendet werden, als Materialien eingebunden in ein Polymernetzwerk oder als Mischungen aus diesen beiden Formen eingesetzt werden. Als Phasenwechselmaterialien in Rohform eignen sich zum Beispiel Polyesteralkohole, Polyetheralkohole oder Polyalkylenoxide. In bevorzugter Ausführungsform werden die Phasenwechselmaterialien eingebunden in ein Polymernetzwerk verwendet. Dieses Polymernetzwerk wird gebildet aus mindestens einem Copolymer auf Basis von mindestens zwei verschiedenen ethylenisch ungesättigten Monomeren (Compound-Komponente C). Zweckmäßig wird der Zusammensetzung ein polymerer Modifikator hinzugefügt, der die thermoplastischen Eigenschaften und die Verarbeitbarkeit verbessert. Der polymere Modifikator ist gewählt aus der Gruppe, umfassend amorphe Polymere wie Cycloolefin-Copolymere (COC), Polymethylmethacrylate (PMMA), amorphes Polypropylen, amorphes Polyamid, amorpher Polyester oder Polycarbonate (PC).Phase change material within the meaning of this invention are all materials selected from the groups mentioned in the previous paragraph, which have a phase transition temperature in the range from -42 °C to +150 °C, in particular from -30 °C to +96 °C, at which their volume or their density changes reversibly. These phase change materials can be used alone (in raw form), as materials integrated into a polymer network or as mixtures of these two forms. Polyester alcohols, polyether alcohols or polyalkylene oxides, for example, are suitable as phase change materials in raw form. In a preferred embodiment, the phase change materials are used bound in a polymer network. This polymer network is formed from at least one copolymer based on at least two different ethylenically unsaturated monomers (compound component C). A polymeric modifier is expediently added to the composition, which improves the thermoplastic properties and the processability. The polymeric modifier is selected from the group comprising amorphous polymers such as cycloolefin copolymers (COC), polymethyl methacrylate (PMMA), amorphous polypropylene, amorphous polyamide, amorphous polyester or polycarbonate (PC).
Gegebenenfalls enthält die Zusammensetzung ein oder mehrere Additiv(e), nachfolgend als Compoundkomponente E bezeichnet, die gewählt sind aus der Gruppe der flammhemmenden Stoffe und/oder der Thermo- und/oder UV-Vis-Licht-Stabilisatoren und/oder der Oxidationsinhibitoren und/oder der Ozoninhibitoren und/oder der Farbstoffe und/oder Farb- und/oder anderen Pigmente und/oder der Schaumerzeuger und/oder der Haftvermittler und/oder der Prozesshilfsmittel und/oder der Vernetzungsmittel und/oder der Dispergierhilfsmittel und/oder der sonstigen Mittel und Füllstoffe, insbesondere Siliciumcarbid, Bornitrid und/oder Aluminiumnitrid zur Erhöhung der Wärmeleitfähigkeit.If appropriate, the composition contains one or more additive(s), referred to below as compound component E, which are selected from the group of flame retardant substances and/or thermal and/or UV-Vis light stabilizers and/or oxidation inhibitors and/or or the ozone inhibitors and/or the dyes and/or dyes and/or other pigments and/or the foam generators and/or the adhesion promoters and/or the processing aids and/or the crosslinking agents and/or the dispersing aids and/or the other agents and Fillers, in particular silicon carbide, boron nitride and/or aluminum nitride to increase thermal conductivity.
Die Zusammensetzung enthält zweckmäßig, bezogen auf ihr Gesamtgewicht, 10 bis 98 Gew.-% Matrixpolymer oder Matrixpolymerblend und in Summe 2 bis 90 Gew.-% Leitfähigkeitsadditiv und Phasenwechselmaterial sowie ggf. weitere Additive. Vorzugsweise enthält sie 15 bis 89 Gew.-% Matrixpolymer oder Matrixpolymerblend und in Summe 11 bis 85 Gew.-% Leitfähigkeitsadditiv und Phasenwechselmaterial sowie ggf. weitere Additive. Besonders bevorzugt enthält die Zusammensetzung 17 bis 50 Gew.-% Matrixpolymer oder Matrixpolymerblend und in Summe 50 bis 83 Gew.-% Leitfähigkeitsadditiv und Phasenwechselmaterial sowie ggf. weitere Additive.The composition expediently contains, based on its total weight, 10 to 98% by weight of matrix polymer or matrix polymer blend and a total of 2 to 90% by weight of conductivity additive and phase change material and optionally further additives. It preferably contains 15 to 89% by weight of matrix polymer or matrix polymer blend and a total of 11 to 85% by weight of conductivity additive and phase change material and optionally other additives. The composition particularly preferably contains 17 to 50% by weight of matrix polymer or matrix polymer blend and a total of 50 to 83% by weight of conductivity additive and phase change material and optionally further additives.
Der Temperaturbereich und die Intensität des PTC-Effektes der aus der Zusammensetzung hergestellten Formkörper können durch Wahl der Bestandteile und deren jeweiligem Masseanteil an die Anwendungserfordernisse angepasst werden.The temperature range and the intensity of the PTC effect of the moldings produced from the composition can be adapted to the application requirements by selecting the components and their respective mass fraction.
Aus der Zusammensetzung lassen sich diverse Formkörper, wie Monofilamente, Multifilamente, Stapelfasern, geschlossenzellige oder offenzellige oder gemischtzellige Schaumstoffe, Integralschäume, klein- und großflächige Schichten, Flecken, Filme oder Folien herstellen. In einer bevorzugten Ausführungsform der Erfindung werden die aus der Zusammensetzung erzeugten Formkörper mit Hilfe von Vernetzungsmitteln und/oder durch Wärmeeinwirkung und/oder energiereiche Strahlung vernetzt, um die elektrischen und thermischen Eigenschaften dauerhaft zu stabilisieren.Various moldings, such as monofilaments, multifilaments, staple fibers, closed-cell or open-cell or mixed-cell foams, integral foams, small and large-area layers, patches, films or foils can be produced from the composition. In a preferred embodiment of the invention, the moldings produced from the composition are crosslinked with the aid of crosslinking agents and/or by the action of heat and/or high-energy radiation in order to permanently stabilize the electrical and thermal properties.
Durch thermoplastische Verarbeitungsprozesse können Formkörper wie Monofilamente, Multifilamente, Stapelfasern, Spinnvliesstoffe, geschlossenzelliger oder offenzelliger oder gemischtzelliger Schaumstoffe, Integralschäume, klein- und großflächiger Schichten, Flecken, Filme, Folien oder Spritzgussformkörper hergestellt werden, die einen positiven Temperaturkoeffizienten des elektrischen Widerstands bzw. PTC-Effekt aufweisen. Mit den erfindungsgemäßen Formkörpern sind Produkte herstellbar, deren elektrischer Widerstand sich beim Anlegen einer vorgegebenen elektrischen Spannung U im Bereich von 0,1 V bis 240 V mit steigender Temperatur in einem definierten Temperaturbereich signifikant erhöht, wodurch der Strom reduziert und die im Produkt verbrauchte elektrische Leistung begrenzt wird.Molded articles such as monofilaments, multifilaments, staple fibers, spunbonded nonwovens, closed-cell or open-celled or mixed-cell foams, integral foams, small and large-area layers, patches, films, foils or injection-molded articles can be produced by thermoplastic processing processes, which have a positive temperature coefficient of electrical resistance or PTC have effect. With the moldings according to the invention, products can be produced whose electrical resistance increases significantly when a predetermined electrical voltage U in the range from 0.1 V to 240 V is applied with increasing temperature in a defined temperature range, which reduces the current and the electrical power consumed in the product is limited.
Die Erfindung wird anhand von Figuren näher erläutert. Es zeigen
- Fig. 1a
- die Stromstärke als Funktion der Zeit in einem Heizgewebe, das PTC-Filamentgarn enthält;
- Fig. 1b
- die Temperatur des Heizgewebes der
Fig. 1a als Funktion der Zeit; - Fig. 2
- den normierten elektrischen Widerstand R(T) / R(24 °C) von PTC-Mono- und Multifilamenten;
- Fig. 1a
- current as a function of time in a heating fabric containing PTC filament yarn;
- Fig. 1b
- the temperature of the heating fabric
Fig. 1a as a function of time; - 2
- the normalized electrical resistance R(T) / R(24 °C) of PTC mono- and multifilaments;
Durch Variation der Compoundkomponenten A, B, C, D und ggf. E lassen sich der Temperaturbereich sowie die Intensität des PTC-Effektes einstellen. Dieses Verhalten dokumentieren die Figuren
In
Zustand auch die Temperatur des Heizgewebes konstant.The temperature of the heating fabric is also constant.
- 1a = "PTC-Monofilament_01a"
- 1b = "PTC-Monofilament_01b"
- 2 = "PTC-Monofilament_02"
- 3 = "PTC-Monofilament_03"
- 4 = "PTC-Monofilament_04"
- 5 = "PTC-Monofilament_05"
- 6 = "PTC-Multifilament_06"
- 7 = "PTC-Monofilament_07"
- 1a = "PTC-Monofilament_01a"
- 1b = "PTC-Monofilament_01b"
- 2 = "PTC-Monofilament_02"
- 3 = "PTC-Monofilament_03"
- 4 = "PTC-Monofilament_04"
- 5 = "PTC-Monofilament_05"
- 6 = "PTC-Multifilament_06"
- 7 = "PTC-Monofilament_07"
Es können je nach Konzentration der Bestandteile der Zusammensetzung Mono- und Multifilamente mit voneinander verschiedener PTC-Charakteristik bzw. Widerstands-Temperatur-Kennlinie erzeugt werden.Depending on the concentration of the components of the composition, mono- and multi-filaments can be produced with different PTC characteristics or resistance-temperature characteristics.
Die mit "PTC-Monofilament_01a" und "PTC-Monofilament_01b" bezeichneten Monofilamente enthalten ein Phasenwechselmaterial (PCM) mit einem Schmelzbereich von 45 °C bis 63 °C und einem Hauptschmelzpeak bei einer Temperatur von 52 °C. Der Anteil des Phasenwechselmaterials lag bei 5,25 Gew.-%. Die beiden Kurven (a) und (b) belegen die gute Reproduzierbarkeit des Herstellungsverfahrens. Obgleich "PTC-Monofilament_01a" und "PTC-Monofilament_01b" unterschiedlichen Filamentspulen entstammen, ist die Abweichung zwischen den Kurven (a) und (b) vernachlässigbar. In den mit "PTC-Monofilament_02" und "PTC-Monofilament_03" bezeichneten Monofilamenten wurde ein Phasenwechselmaterial mit einem Hauptschmelzpeak bei einer Temperatur von 35 °C, respektive von 28 °C eingesetzt. Der PTC-Effekt ist mithin in beiden Monofilamenten bereits bei entsprechend niedrigen Temperaturen im Vergleich zu "PTC-Monofilament_01" zu beobachten. In den mit "PTC-Monofilament_05", "PTC-Monofilament_04" und "PTC-Monofilament_07" bezeichneten Monofilamenten wurde das gleiche Phasenwechselmaterial wie im Fall der Probe "PTC-Monofilament_01" jeweils mit einem Gewichtsanteil von 5,25 Gew.-% eingesetzt, d. h. das Phasenwechselmaterial wies einen Hauptschmelzpeak bei einer Temperatur von T = 52 °C auf. Die Monofilamente "PTC-Monofilament_05", "PTC-Monofilament_04" und "PTC-Monofilament_07" unterscheiden sich jedoch in ihrer elektrischen Leitfähigkeit, da die Art, die Zusammensetzung und der Anteil der Leitfähigkeitskomponente B jeweils variiert ist. Dies wirkt sich auf das Ausgangsniveau des elektrischen Widerstands der Filamente bei 24 °C signifikant aus. So betrug der Widerstand des Monofilaments "PTC-Monofilament_07" nur R = 0,6 MΩ/m, während der Widerstand von "PTC-Monofilament_04" bei 17,9 MΩ/m, von "PTC-Monofilament_05" bei R = 22,0 MΩ/m und von "PTC-Monofilament_01" bei R = 26,1 MΩ/m liegt. Bei der Probe mit der Bezeichnung "PTC-Multifilament_06" handelt es sich um ein Multifilament mit einer Feinheit von 307 dtex f36. Für dessen Herstellung wurde ein Material gewählt, das auf Grund der Art und des Anteils der Leitfähigkeitskomponente B zu einer relativ guten spezifischen elektrischen Leitfähigkeit führt und zugleich die Herstellung von Multifilamenten gestattet. Bei 24 °C betrug der elektrische Widerstand des Multifilamentgarns "PTC-Multifilament_06" 13,1 MΩ/m und war somit im Vergleich zu den Monofilamenten mit einer Feinheit von 760 dtex und einem Durchmesser von 300 µm vergleichsweise niedrig. Die PTC-Intensität des Multifilamentgarns entsprach im Wesentlichen dem an Monofilamenten beobachteten Verhalten.The monofilaments designated "PTC-Monofilament_01a" and "PTC-Monofilament_01b" contain a phase change material (PCM) with a melting range of 45 °C to 63 °C and a main melting peak at a temperature of 52 °C. The proportion of the phase change material was 5.25% by weight. The two curves (a) and (b) demonstrate the good reproducibility of the manufacturing process. Although "PTC-Monofilament_01a" and "PTC-Monofilament_01b" come from different filament spools, the deviation between curves (a) and (b) is negligible. A phase change material with a main melting peak at a temperature of 35 °C and 28 °C, respectively, was used in the monofilaments designated "PTC-Monofilament_02" and "PTC-Monofilament_03". The PTC effect can therefore be observed in both monofilaments at correspondingly low temperatures compared to "PTC-Monofilament_01". In the monofilaments designated "PTC-Monofilament_05", "PTC-Monofilament_04" and "PTC-Monofilament_07", the same phase change material as in the case of sample "PTC-Monofilament_01" was used, each with a weight proportion of 5.25% by weight, i.e. H. the phase change material showed a main melting peak at a temperature of T = 52 °C. However, the monofilaments "PTC-Monofilament_05", "PTC-Monofilament_04" and "PTC-Monofilament_07" differ in their electrical conductivity, since the type, composition and proportion of the conductivity component B varies in each case. This has a significant impact on the initial level of electrical resistance of the filaments at 24 °C. The resistance of the monofilament "PTC-Monofilament_07" was only R = 0.6 MΩ/m, while the resistance of "PTC-Monofilament_04" was 17.9 MΩ/m and of "PTC-Monofilament_05" was R = 22.0 MΩ/m and of "PTC-Monofilament_01" at R = 26.1 MΩ/m. The sample with the designation "PTC-Multifilament_06" is a multifilament with a fineness of 307 dtex f36. A material was chosen for its production which, due to the type and proportion of the conductivity component B, leads to a relatively good specific electrical conductivity and at the same time allows the production of multifilaments. At 24 °C, the electrical resistance of the multifilament yarn "PTC-Multifilament_06" was 13.1 MΩ/m and was therefore comparatively low compared to the monofilaments with a fineness of 760 dtex and a diameter of 300 µm. The PTC intensity of the multifilament yarn essentially corresponded to the behavior observed with monofilaments.
Die Einsatzmöglichkeiten und Anwendungen der erfindungsgemäßen Formkörper mit PTC sind vielfältig, da sie sowohl mit niedrigen Spannungen von 0,1 Volt bis 42 Volt als auch mit relativ hohen elektrischen Spannungen von bis zu 240 Volt sowie mit Gleich- oder Wechselspannung und Frequenzen von bis zu 1 Megahertz beaufschlagt werden können und dauerhaft stabile elektrische und thermische Eigenschaften aufweisen.The possible uses and applications of the moldings according to the invention with PTC are diverse, since they can be charged with low voltages from 0.1 volts to 42 volts as well as with relatively high electrical voltages of up to 240 volts, as well as with direct or alternating voltage and frequencies of up to 1 megahertz and permanently stable electrical and have thermal properties.
Als Leitfähigkeitsadditiv wird vorzugsweise Ruß verwendet. Im Rahmen der vorliegenden Erfindung werden die Begriffe "Ruß" und "Carbon Black" synonym verwendet. Carbon Black wird nach verschiedenen Verfahren hergestellt. Je nach Herstellungsverfahren oder Ausgangsmaterial wird der erhaltene Ruß auch als "Furnace Black", "Acetylene Black", "Plasma Black" oder "Activated Carbon" bezeichnet. Carbon Black besteht aus sogenannten primären Rußartikeln mit einem mittleren Durchmesser im Bereich von 15 bis 300 nm. Bedingt durch das Herstellungsverfahren bildet jeweils eine Vielzahl von primären Rußpartikeln ein sogenanntes Rußaggregat, in dem benachbarte primäre Rußpartikel durch mechanisch sehr stabile Sinterbrücken miteinander verbunden sind. Aufgrund elektrostatischer Anziehung verklumpen die Rußaggregate zu mehr oder minder stark gebundenen Agglomeraten. Je nach Lieferant des Carbon Black werden die Rußaggregate und -agglomerate gegebenenfalls zusätzlich granuliert oder pelletisiert.Carbon black is preferably used as the conductivity additive. In the context of the present invention, the terms “soot” and “carbon black” are used synonymously. Carbon black is manufactured using a variety of processes. Depending on the manufacturing process or starting material, the carbon black obtained is also referred to as "Furnace Black", "Acetylene Black", "Plasma Black" or "Activated Carbon". Carbon black consists of so-called primary soot particles with an average diameter in the range of 15 to 300 nm. Due to the manufacturing process, a large number of primary soot particles form a so-called soot aggregate in which neighboring primary soot particles are connected to one another by mechanically very stable sinter bridges. Due to electrostatic attraction, the carbon black aggregates form more or less strongly bound agglomerates. Depending on the supplier of the carbon black, the soot aggregates and agglomerates may also be granulated or pelletized.
Bei der Verarbeitung von Polymerzusammensetzungen, die Carbon Black als Additiv enthalten, in Schmelzverfahren, wie Extrusion, Schmelzspinnen und Spritzguss sind die Rußaggregate und -agglomerate Scherkräften ausgesetzt. Die in einer polymeren Schmelze einwirkende maximale Scherkraft hängt in komplexer Weise von der Geometrie und den Betriebsparametern des verwendeten Extruders oder Gelieraggregats sowie von den rheologischen Eigenschaften der polymeren Zusammensetzung und dessen Temperatur ab. Die im Schmelzverfahren einwirkende maximale Scherkraft kann die elektrostatische Bindungskraft übersteigen und Rußagglomerate in Rußaggregate aufspalten, die in der Schmelze dispergiert werden. Andererseits kann in niederviskosen polymeren Schmelzen oder Lösungen mit hoher Beweglichkeit der Rußaggregate und geringer Scherkraft eine verstärkte Agglomeration bzw. Flokkulation auftreten.During the processing of polymer compositions containing carbon black as an additive in melt processes such as extrusion, melt spinning and injection molding, the carbon black aggregates and agglomerates are subjected to shear forces. The maximum shear force acting in a polymeric melt depends in a complex manner on the geometry and operating parameters of the extruder or gelling unit used, as well as on the rheological properties of the polymeric composition and its temperature. The maximum shear force experienced in the melt process can exceed the electrostatic binding force and break down carbon black agglomerates into carbon black aggregates that are dispersed in the melt. On the other hand, increased agglomeration or flocculation can occur in low-viscosity polymer melts or solutions with high mobility of the carbon black aggregates and low shearing force.
Die Leitfähigkeit eines Carbon Black enthaltenden Polymerformkörpers ist maßgeblich durch den Anteil und die Verteilung und Morphologie der Rußagglomerate und -aggregate beeinflußt. Wie vorstehend erläutert, hängt die Verteilung und Morphologie von Carbon Black in einem durch Schmelzverfahren erzeugten Polymerformkörper von der Beschaffenheit des Carbon Black Additivs, den rheologischen Eigenschaften der Polymerzusammensetzung und den Verfahrensparametern ab. Je nach Anteil und Beschaffenheit des Carbon Black Additivs und der weiteren Komponenten der Polymerzusammensetzung sind die Verfahrensparameter in geeigneter Weise derart anzupassen, dass der Formkörper die vorgegebene Leitfähigkeit aufweist. Der Einfluß und die Wechselwirkung zwischen den physikalischen Eigenschaften des Carbon Black Additivs, den weiteren Bestandteilen der Polymerzusammensetzung und den Verfahrensparametern ist äußerst komplex und bis dato nur unzureichend verstanden.The conductivity of a polymer molding containing carbon black is decisively influenced by the proportion and the distribution and morphology of the carbon black agglomerates and aggregates. As discussed above, the distribution and morphology of carbon black in a melt-processed polymer molding depends on the nature of the carbon black additive, the rheological properties of the polymer composition, and the process parameters. Depending on the proportion and nature of the carbon black additive and the other components of the polymer composition, the process parameters must be suitably adjusted in such a way that the shaped body has the specified conductivity. The influence and the interaction between the physical properties of the carbon black additive, the other components of the polymer composition and the process parameters is extremely complex and up to now only insufficiently understood.
In der Fachliteratur finden sich Hinweise, dass das Aufbrechen von Rußagglomeraten und eine gleichförmge Dispersion von Rußaggregaten aufgrund hoher Scherkräfte in Polymerschmelzen die Ausbildung eines Netzwerkes aus Rußagglomeraten verhindert und eine Reduktion der Leitfähigkeit um mehrere Größenordnungen bewirkt.There are indications in the technical literature that the breaking up of carbon black agglomerates and a uniform dispersion of carbon black aggregates due to high shear forces in polymer melts prevents the formation of a network of carbon black agglomerates and causes a reduction in conductivity by several orders of magnitude.
Überraschenderweise legen die von den Erfindern durchgeführten Versuche den Schluß nahe, dass unter Einsatz von Phasenwechselmaterialien in diversen Polymermatrizes sich eine feine und gleichförmige Dispersion von Rußagglomeraten und -aggregaten in Polymerformkörpern erreichen lässt und sich die Leitfähigkeit verbessert. Damit ist es gelungen Polymerformkörper herzustellen, die bei einer vorgegebenen Obergrenze von 30 Gew.-% für den Carbon Black Anteil eine Leitfähigkeit von bis zu 100 S/m (entsprechend einem spezifischen Widerstand ρ = 0,01 Ω·m) und in besonderen Fällen von bis zu 1000 S/m (p = 0,001 Ω·m) aufweisen.Surprisingly, the experiments carried out by the inventors suggest that using phase change materials in various polymer matrices can achieve a fine and uniform dispersion of carbon black agglomerates and aggregates in polymer moldings and improve conductivity. It has thus been possible to produce polymer moldings which, with a specified upper limit of 30% by weight for the carbon black content, have a conductivity of up to 100 S/m (corresponding to a specific resistance ρ = 0.01 Ω m) and in special cases of up to 1000 S/m (p = 0.001 Ω m).
In den nachfolgenden Beispielen wurden sämtliche Ausgangsmaterialien bzw. Komponenten, d. h. alle Polymere, Polymerblends und Additive erst nach sorgfältiger Trocknung in Vakuumtrockenschränken verarbeitet. Wie bereits vorstehend erläutert, kann das Phasenwechselmaterial einen oder mehrere Stoffe umfassen. In den Beispielen umfasst das Phasenwechselmaterial eine als Netzwerkbildner und Stabilisator fungierende Compoundkomponente C sowie eine Compoundkomponente D, bei der es sich um einen Stoff, insbesondere um ein Paraffin mit einem Phasenübergang in einem Temperaturbereich von etwa 20 °C bis etwa 100 °C handelt. Prozente sind Gewichtsprozente, soweit nicht anders angegeben oder aus dem Zusammenhang unmittelbar ersichtlich.In the following examples, all starting materials or components, i. H. All polymers, polymer blends and additives are only processed after careful drying in vacuum drying cabinets. As already explained above, the phase change material can comprise one or more substances. In the examples, the phase change material comprises a compound component C that functions as a network former and stabilizer, and a compound component D that is a substance, in particular a paraffin, with a phase change in a temperature range from about 20° C. to about 100° C. Percentages are percentages by weight unless otherwise stated or immediately apparent from the context.
Das Matrixpolymer bzw. die Compoundkomponente A besteht aus einem Gemisch mit einem Anteil von 39,8 Gew.-% an Polypropylen des Typs Moplen® 462 R und Polyethylen niedriger Dichte (LDPE) des Typs Lupolen® mit einem Anteil von 22,5 Gew.-% und als Leitfähigkeitsadditiv bzw. Compoundkomponente B mit einem Anteil von 22,5 Gew.-% wurde ein Leitruß (Carbon Black) vom Typ "Super Conductive Furnace N 294" eingesetzt. Die Compoundkomponente C bestand aus einem Blend aus Styrol-Blockcopolymer und Poly(methylmethacrylat), jeweils mit einem Anteil von 2,25 Gew.-%. Als Compoundkomponente D bzw. Phasenwechselmaterial im engeren Sinn wurde 10,5 Gew.-% Paraffin des Typs Rubitherm RT52 mit einem Hauptschmelzpeak bei einer Temperatur von 52 °C eingesetzt. Als weitere Compoundkomponente E mit einem Anteil von 0,2 Gew.-% wurde eine Mischung von 0,06 Gew-% Irganox® 1010 (0,06%), 0,04 Gew.-% Irgafos® 168 (0,04 Masse%) und 0,10 Gew.-% Calciumstearat verwendet.The matrix polymer or compound component A consists of a mixture with a proportion of 39.8% by weight of polypropylene of the Moplen ® 462 R type and low-density polyethylene (LDPE) of the Lupolen ® type with a proportion of 22.5% by weight. -% and as A conductive carbon black of the “Super Conductive Furnace N 294” type was used as conductivity additive or compound component B with a proportion of 22.5% by weight. Compound component C consisted of a blend of styrene block copolymer and poly(methyl methacrylate), each with a proportion of 2.25% by weight. 10.5% by weight of Rubitherm RT52 paraffin with a main melting peak at a temperature of 52° C. was used as compound component D or phase change material in the narrower sense. A mixture of 0.06% by weight Irganox® 1010 (0.06%), 0.04% by weight Irgafos® 168 (0.04% by mass %) and 0.10% by weight of calcium stearate.
Zunächst wird in einem separaten Schritt die Compoundkomponente D, d. h. das Paraffin zusammen mit dem Styrol-Blockcopolymer und dem Poly(methylmethacrylat) in einem mit einem Granulator ausgerüsteten Knetaggregat plastifiziert, homogenisiert und anschließend granuliert. Das PCM-Granulat hatte die folgende Zusammensetzung:
- 70 ∗Gew.-% PCM (Rubitherm RT52, Rubitherm Technologies GmbH);
- 15 ∗Gew.-% SEEPS (Styrol-Blockcopolymer vom Septon® -Typ, Kuraray Co. Ltd);
- 15 ∗Gew.-% PMMA (PMMA Typ 7N natur, Evonik AG);
- 70 * % by weight PCM (Rubitherm RT52, Rubitherm Technologies GmbH);
- 15 ∗ wt% SEEPS (Septon ® type styrenic block copolymer, Kuraray Co. Ltd);
- 15 ∗ % by weight PMMA (PMMA type 7N natural, Evonik AG);
Dieses PCM-Granulat, die Matrixpolymere Polypropylen (Moplen® 462 R) in Granulatform und Polyethylen (LDPE Lupolen®) in Granulatform sowie die Compoundkomponente E wurden miteinander gemischt und in einem Extruderhopper vorgelegt. Der Leitruß bzw. die Compoundkomponente B wurde in einer mit dem Extruder verbundenen Dosiereinrichtung vorgelegt. Die Dosiereinrichtung ermöglicht es, den Leitruß gleichförmig in die Polymerschmelze einzubringen. Bei dem Extruder handelt es sich um einen gleichläufigen Doppelschneckenextruder Rheomex PTW 16/25 der Firma Haake mit Standardkonfiguration, d. h. mit segmentierten Schnecken ohne Rückführelemente. Mit dem Extruder wurden der Hopperinhalt und der Leitruß plastifiziert, homogenisiert und extrudiert. Während des gesamten Extrusionsprozesses wurden der Hopperextruder und die Dosiereinrichtung mit Stickstoff geflutet. Die Schneckenumdrehungszahl betrug 180 U/min und der Massedurchsatz lag bei etwa 1 kg/h. Die Temperatur der Extruderzonen lag bei den folgendn Werten: 220 °C am Einzug, 240 °C in Zone 1, 260 °C in Zone 2, 240 °C in Zone 3 und 220 °C an der Strangdüse. Der Innendurchmesser der Strangdüse betrug 3 mm. Der extrudierte und erkaltete Polymerstrang wurde in einem Granulator granuliert. Das derart gewonnene Polymergranulat hatte die folgende Zusammensetzung:
Dieses Granulat wurde getrocknet und diente als Ausgangsmaterial für die Herstellung von Monofilamenten auf einer Filamentextrusionsanlage der Firma FET Ltd. Leeds. Die Filamentextrusionsanlage umfasst einen Einschneckenextruder mit einem Schneckendurchmesser von 25 mm und einem Länge-zu-Durchmesser-Verhältnis von L/D = 30 : 1. Der Massedurchsatz an Polymerschmelze betrug 13,7 g/min. Es wurde folgendes Massetemperaturregime realisiert: 200 °C in Zone 1, 210 °C in Zone 2, 220 °C in Zone 3, 230 °C in Zone 4, 240 °C in Zone 5, 250 °C in Zone 6 und 260 °C an der Filamentdüse. Der Düsenlochdurchmesser betrug 1 mm. Die extrudierte Polymerschmelze wurde in einem Wasserbad mit einer Temperatur von 20 °C abgekühlt und das verfestigte Monofilament in einem Prozessschritt "online" mit drei Reckwerken gereckt. Hierbei betrug die Umfangsgeschwindigkeit der Galetten des ersten Reckwerks 58,2 m/min und die des des zweiten Reckwerks 198 m/min. Ein zwischen dem ersten und zweiten Reckwerk angeordnetes Reckbad enthielt Wasser mit einer Temperatur von 90 °C. Nach dem zweiten Reckwerk wurde das Monofilament durch einen Heizofen auf das dritte Reckwerk geführt. Die Umfangsgeschwindigkeit der Galetten des dritten Reckwerks betrug ebenfalls 198 m/min. Das gereckte Monofilament wurde dann auf eine Hülse des Typs "K 160" gewickelt. Der Wickler wurde mit einer Geschwindigkeit von 195 m/min betrieben. Der Reckgrad betrug 1 : 3,4. Der Durchmesser des derart hergestellten Monofilaments beträgt 300 µm.This granulate was dried and served as the starting material for the production of monofilaments on a FET Ltd. filament extrusion plant. leeds The filament extrusion system comprises a single-screw extruder with a screw diameter of 25 mm and a length-to-diameter ratio of L/D=30:1. The mass throughput of polymer melt was 13.7 g/min. The following melt temperature regime was implemented: 200 °C in
Die Charakterisierung des Monofilaments hinsichtlich seiner textilphysikalischen Eigenschaften ergab eine Höchstzugkraftdehnung von 23 %, eine Zugfestigkeit von 62 mN/tex und einen Anfangsmodul von 1024 MPa.The characterization of the monofilament with regard to its physical textile properties showed a maximum elongation at break of 23%, a tensile strength of 62 mN/tex and an initial modulus of 1024 MPa.
Der elektrische Widerstand des Monofilaments in Abhängigkeit von der Temperatur wurde mit einer in einer Klimakammer angeordneten Vier-Spitzen-Vorrichtung gemessen. Hierbei wurde die Temperatur schrittweise von 24 °C (Raumtemperatur) auf Werte von 30 °C, 40 °C, 50 °C, 60 °C, 70 °C und 80 °C erhöht. Die Messung wurde simultan an 8 Teilstücken des Monofilaments mit einer Messtrecke bzw. -länge von jeweils 75 mm durchgeführt. Der elektrische Widerstand des Monofilaments hat bei Raumtemperatur den Wert R(24 °C) = 2,6 MΩ/m. Durch Aufheizen des Monofilaments auf eine Temperatur von 80 °C erhöht sich der Widerstand auf einen Wert von R(80 °C) = 19,0 MΩ/m. Nach dem Abkühlen des Monofilaments auf Zimmertemperatur stellte sich der Anfangswiderstand wieder ein. Das in der
Als Matrixpolymer bzw. Compoundkomponente A wurde ein Blend mit einem Anteil von 34,3 Gew.-% Polypropylen des Typs Moplen® 462 R und Polyethylen niedriger Dichte (LDPE) des Typs Lupolen® mit einem Anteil von 30 Gew.-% sowie als Leitfähigkeitsadditiv bzw. Compoundkomponente B mit einem Anteil von 28,0 Gew.-% ein Leitruß (Carbon Black) vom Typ "Super Conductive Furnace N 294" eingesetzt. Die Compoundkomponente C bestand aus einem Blend aus Styrol-Blockcopolymer und Poly(methylmethacrylat), jeweils mit einem Anteil von 1,125 Gew.-%. Als Compoundkomponente D bzw. Phasenwechselmaterial im engeren Sinn wurde 5,25 Gew.-% Paraffin des Typs Rubitherm RT55 mit einem Hauptschmelzpeak bei einer Temperatur von 55 °C eingesetzt. Als weitere Compoundkomponente E mit einem Anteil von 0,2 Gew.-% wurde eine Mischung von 0,06 Gew-% Irganox® 1010 (0,06%), 0,04 Gew.-% Irgafos® 168 (0,04 Masse%) und 0,10 Gew.-% Calciumstearat verwendet.A blend with a proportion of 34.3% by weight of polypropylene of the Moplen® 462 R type and low-density polyethylene (LDPE) of the type Lupolen® with a proportion of 30% by weight and as a conductivity additive was used as the matrix polymer or compound component A or compound component B with a proportion of 28.0% by weight of a conductive carbon black (carbon black) of the "Super Conductive Furnace N 294" type. Compound component C consisted of a blend of styrene block copolymer and poly(methyl methacrylate), each with a proportion of 1.125% by weight. 5.25% by weight of Rubitherm RT55 paraffin with a main melting peak at a temperature of 55° C. was used as compound component D or phase change material in the narrower sense. A mixture of 0.06% by weight Irganox® 1010 (0.06%), 0.04% by weight Irgafos® 168 (0.04% by mass %) and 0.10% by weight of calcium stearate.
Zunächst wird in einem separaten Schritt in einem mit einem Granulator ausgerüsteten Knetaggregat ein PCM-Granulat, bestehend aus Paraffin als Phasenwechselmaterial sowie Styrol-Blockcopolymer und Poly(methylmethacrylat) als Bindemittel bzw. Stabilisator hergestellt. Das PCM-Granulat hatte die folgende Zusammensetzung:
- 70 ∗Gew.-% PCM (Rubitherm RT55, Rubitherm Technologies GmbH);
- 15 ∗Gew.-% SEEPS (Styrol-Blockcopolymer vom Septon® -Typ, Kuraray Co. Ltd);
- 15 ∗Gew.-% PMMA (PMMA Typ 7N natur, Evonik AG);
- 70 * % by weight PCM (Rubitherm RT55, Rubitherm Technologies GmbH);
- 15 ∗ wt% SEEPS (Septon ® type styrenic block copolymer, Kuraray Co. Ltd);
- 15 ∗ % by weight PMMA (PMMA type 7N natural, Evonik AG);
Dieses PCM-Granulat, die Matrixpolymere Polyethylen (LDPE Lupolen®) in Granulatform, Polypropylen (Moplen® 462 R) in Granulatform und die Compoundkomponente E wurden miteinander gemischt und in einem Extruderhopper vorgelegt. Der Leitruß bzw. die Compoundkomponente B wurde in einer mit dem Extruder verbundenen Dosiereinrichtung vorgelegt. Die Dosiereinrichtung ermöglicht es, den Leitruß gleichförmig in die Polymerschmelze einzubringen. Bei dem Extruder handelt es sich um einen gleichläufigen Doppelschneckenextruder Rheomex PTW 16/25 der Firma Haake mit Standardkonfiguration, d. h. mit segmentierten Schnecken ohne Rückführelemente. Mit dem Extruder wurden der Hopperinhalt und der Leitruß plastifiziert, homogenisiert und extrudiert. Während des gesamten Extrusionsprozesses wurden der Hopperextruder und die Dosiereinrichtung mit Stickstoff geflutet. Die Schneckenumdrehungszahl betrug 180 U/min und der Massedurchsatz lag bei etwa 1 kg/h. Die Temperatur der Extruderzonen lag bei den folgendn Werten: 220 °C am Einzug, 240 °C in Zone 1, 260 °C in Zone 2, 240 °C in Zone 3 und 220 °C an der Strangdüse. Der Innendurchmesser der Strangdüse betrug 3 mm. Der extrudierte und erkaltete Polymerstrang wurde in einem Granulator granuliert. Das derart gewonnene Granulat hatte die folgende Zusammensetzung:
Dieses Granulat wurde getrocknet und diente als Ausgangsmaterial für die Herstellung von Multifilamentgarn auf einer Filamentextrusionsanlage der Firma FET Ltd. Leeds. Die Verarbeitung des Granulats erfolgte auf einer Filamentextrusionsanlage der Firma FET Ltd. Leeds. Die Filamentextrusionsanlage umfasst einen Einschneckenextruder mit einem Schneckendurchmesser von 25 mm und einem Länge-zu-Durchmesser-Verhältnis von L/D = 30 : 1. Der Massedurchsatz an Polymerschmelze betrug 20 g/min. Es wurde folgendes Massetemperaturregime realisiert: 190 °C in Zone 1, 190 °C in Zone 2, 190 °C in Zone 3, 190 °C in Zone 4, 190 °C in Zone 5, 190 °C in Zone 6 und 190 °C an der Spinndüse. Die Spinndüse weist 36 Bohrungen mit einem Lochdurchmesser von jeweils 200 µm auf. Die aus der Spindüse austretende Polymerschmelze wurde in einem Kühlschacht bei einer Lufttemperatur von 25 °C abgekühlt und das so verfestigte Multifilament in einem Prozessschritt "online" über vier Galettenpaare gereckt. Dabei betrug die Umfangsgeschwindigkeit der Abzugsgalette 592 m/min, des ersten Galettenpaares 594 m/min, des zweiten Galettenpaares 596 m/min, des dritten Galettenpaares 598 m/min und des vierten Galettenpaares 600 m/min. Die Multifilamente wurden anschließend auf eine Hülse des Typs "K 160" gewicklt. Der Wickler wurde mit einer Wickelgeschwindigkeit von 590 m/min betrieben. Das erhaltene Multifilamentgarn wies eine Feinheit von 307 dtex f36 auf.This granulate was dried and served as the starting material for the production of multifilament yarn on a FET Ltd. filament extrusion plant. leeds The granules were processed on a FET Ltd. filament extrusion system. leeds The filament extrusion system comprises a single-screw extruder with a screw diameter of 25 mm and a length-to-diameter ratio of L/D=30:1. The mass throughput of polymer melt was 20 g/min. The following melt temperature regime was implemented: 190 °C in
In einem nachgeschalteten Prozessschritt wurde das Multifilamentgarn mit einem dreistufigen Reckwerk nachgereckt. Die Umfangsgeschwindigkeit der Galetten der ersten Reckstufe betrug 60 m/min und die der zweiten und dritten Reckstufe jeweils 192 m/min. Zwischen der ersten und zweite Reckstufe wurde das Multifilament durch ein mit Wasser gefülltes Reckbad mit einer Temperatur von 90 °C geführt. Zwischen der zweiten und dritten Reckstufe wurde das Multifilamentgarn durch einen Heiztunnel geführt. Abschließend wurde das Multifilamentgarn auf eine Hülse des Typs "K 160" gewickelt. Der Wickler wurde mit einer Wickelgeschwindigkeit von 190 m/min betriebene. Der Reckgrad des derart behandelten Multifilmentgarns mit einer Feinheit von 96 dtex f36 betrug 1 : 3,2.In a downstream process step, the multifilament yarn was post-stretched using a three-stage stretching unit. The circumferential speed of the godets in the first stretching stage was 60 m/min and those in the second and third stretching stages were 192 m/min in each case. Between the In the first and second stretching stage, the multifilament was passed through a water-filled stretching bath at a temperature of 90.degree. Between the second and third drawing stage, the multifilament yarn was passed through a heating tunnel. Finally, the multifilament yarn was wound onto a "K 160" type tube. The winder was operated at a winding speed of 190 m/min. The degree of stretching of the multifilm yarn treated in this way with a fineness of 96 dtex f36 was 1:3.2.
Die Charakterisierung des derart prozessierten Multifilamentglattgarns hinsichtlich seiner textilphysikalischen Eigenschaften ergab eine Höchstzugkraftdehnung von 19 %, eine Zugfestigkeit von 136 mN/tex und einen Anfangsmodul von 1431 MPa. Der Durchmesser der Einzelfilamente des Multifilamentsgarns betrug 17 µm.The characterization of the multifilament flat yarn processed in this way with regard to its textile-physical properties showed a maximum elongation at break of 19%, a tensile strength of 136 mN/tex and an initial modulus of 1431 MPa. The diameter of the individual filaments of the multifilament yarn was 17 μm.
An dem nicht nachverstreckten Multifilametgarn mit einer Feinheit von 307 dtex f36 wurde eine Höchstzugkraftdehnung von 192 %, eine Zugfestigkeit von 38 mN/tex und Anfangsmodul von 1190 MPa gemessen. Der Durchmesser der Einzelfilamente des nicht nachverstreckten Multifilamentgarns betrug 31 µm.A maximum elongation at break of 192%, a tensile strength of 38 mN/tex and an initial modulus of 1190 MPa were measured on the non-postdrawn multifilament yarn with a fineness of 307 dtex f36. The diameter of the individual filaments of the multifilament yarn that was not post-drawn was 31 μm.
Der elektrische Widerstand des nicht verstreckten Multifilamentgarns in Abhängigkeit von der Temperatur wurde mit einer in einer Klimakammer angeordneten Vier-Spitzen-Vorrichtung gemessen. Hierbei wurde die Temperatur schrittweise von 24 °C (Raumtemperatur) auf Werte von 30 °C, 40 °C, 50 °C, 60 °C, 70 °C und 80 °C erhöht. Die Messung wurde simultan an 8 Teilstücken des Multifilamentgarns mit einer Messtrecke bzw. -länge von jeweils 75 mm durchgeführt. Der elektrische Widerstand des Multifilamentgarns hat bei Raumtemperatur den Wert R(24 °C) = 13 MΩ/m. Durch Aufheizen des Multifilamentgarns auf eine Temperatur von 80 °C erhöht sich der Widerstand auf einen Wert von R(80 °C) = 119 MΩ/m. Nach dem Abkühlen des Multifilamentgarns auf Zimmertemperatur stellte sich der Anfangswiderstand wieder ein. Das in der
Zur Herstellung dieses Multifilamentgarns wurde eine Polymerzusammensetzung gewählt, die auf Grund des Anteils sowie der Art der Leitfähigkeitskomponente B zu einer relativ guten spezifischen elektrischen Leitfähigkeit führte und aus der dennoch reckbare Multifilamente herstellbar waren. Der elektrische Widerstand des Multifilamentgarns mit einer Feinheit von 307 dtex f36 bei einer Temperatur von 24 °C ist im Vergleich zu dem Monofilament mit einer Feinheit von 760 dtex (Durchmesser 300 µm) bezogen auf die Feinheit bzw. Querschnittsfläche um einen Faktor von 4,6 geringer. Wie aus
Als Matrixpolymer bzw. Compoundkomponente A wurde ein Blend mit einem Anteil von 34,3 Gew.-% Polypropylen des Typs Moplen® 462 R und Polyethylen niedriger Dichte (LDPE) des Typs Lupolen® mit einem Anteil von 30 Gew.-%,als Leitfähigkeitsadditiv bzw. Compoundkomponente B mit einem Anteil von 28,0 Gew.-% ein Leitruß (Carbon Black) vom Typ "Super Conductive Furnace N 294" eingesetzt. Die Compoundkomponente C bestand aus einem Blend aus Styrol-Blockcopolymer und Poly(methylmethacrylat), jeweils mit einem Anteil von 1,125 Gew.-%. Als Compoundkomponente D bzw. Phasenwechselmaterial im engeren Sinn wurde 5,25 Gew.-% Paraffin des Typs Rubitherm RT55 mit einem Hauptschmelzpeak bei einer Temperatur von 55 °C eingesetzt. Als weitere Compoundkomponente E mit einem Anteil von 0,2 Gew.-% wurde eine Mischung von 0,06 Gew-% Irganox® 1010 (0,06%), 0,04 Gew.-% Irgafos® 168 (0,04 Masse%) und 0,10 Gew.-% Calciumstearat verwendet.A blend with a proportion of 34.3% by weight of polypropylene of the Moplen® 462 R type and low-density polyethylene (LDPE) of the Lupolen® type with a proportion of 30% by weight as a conductivity additive was used as the matrix polymer or compound component A or compound component B with a proportion of 28.0% by weight of a conductive carbon black (carbon black) of the "Super Conductive Furnace N 294" type. Compound component C consisted of a blend of styrene block copolymer and poly(methyl methacrylate), each with a proportion of 1.125% by weight. 5.25% by weight of Rubitherm RT55 paraffin with a main melting peak at a temperature of 55° C. was used as compound component D or phase change material in the narrower sense. A mixture of 0.06% by weight Irganox® 1010 (0.06%), 0.04% by weight Irgafos® 168 (0.04% by mass %) and 0.10% by weight of calcium stearate.
Zunächst wird in einem separaten Schritt in einem mit einem Granulator ausgerüsteten Knetaggregat ein PCM-Granulat, bestehend aus Paraffin als Phasenwechselmaterial sowie Styrol-Blockcopolymer und Poly(methylmethacrylat) als Bindemittel bzw. Stabilisator hergestellt. Das PCM-Granulat hatte die folgende Zusammensetzung:
- 70 ∗Gew.-% PCM (Rubitherm RT55, Rubitherm Technologies GmbH);
- 15 ∗Gew.-% SEEPS (Septon® 4055, Kuraray Co. Ltd);
- 15 ∗Gew.-% PMMA (PMMA Typ 7N natur, Evonik AG);
- 70 * % by weight PCM (Rubitherm RT55, Rubitherm Technologies GmbH);
- 15 * wt% SEEPS ( Septon® 4055, Kuraray Co. Ltd);
- 15 ∗ % by weight PMMA (PMMA type 7N natural, Evonik AG);
Dieses PCM-Granulat, die Matrixpolymere Polyethylen (LDPE Lupolen®) in Granulatform, Polypropylen (Moplen® 462 R) in Granulatform und die Compoundkomponente E wurden miteinander gemischt und in einem Extruderhopper vorgelegt. Der Leitruß bzw. die Compoundkomponente B wurde in einer mit dem Extruder verbundenen Dosiereinrichtung vorgelegt. Die Dosiereinrichtung ermöglicht es, den Leitruß gleichförmig in die Polymerschmelze einzubringen. Bei dem Extruder handelt es sich um einen gleichläufigen Doppelschneckenextruder Rheomex PTW 16/25 der Firma Haake mit Standardkonfiguration, d. h. mit segmentierten Schnecken ohne Rückführelemente. Mit dem Extruder wurden der Hopperinhalt und der Leitruß plastifiziert, homogenisiert und extrudiert. Während des gesamten Extrusionsprozesses wurden der Hopperextruder und die Dosiereinrichtung mit Stickstoff geflutet. Die Schneckenumdrehungszahl betrug 180 U/min und der Massedurchsatz lag bei etwa 1 kg/h. Die Temperatur der Extruderzonen lag bei den folgendn Werten: 220 °C am Einzug, 240 °C in Zone 1, 260 °C in Zone 2, 240 °C in Zone 3 und 220 °C an der Strangdüse. Der Innendurchmesser der Strangdüse betrug 3 mm. Der extrudierte und erkaltete Polymerstrang wurde in einem Granulator granuliert. Das derart gewonnene Granulat hatte die folgende Zusammensetzung:
Dieses Granulat wurde in einer Planetenkugelmühle unter Stickstoffflutung zu Pulver vermahlen und das erhaltene Puver 16 Stunden im Vakuumtrockenschrank getrocknet. Das getrocknete Pulver diente als Ausgangsmaterial für die Herstellung von Folie mit einem vertikalen Einschneckenextruder des Typs "Randcastle Microtruder" mit sieben regelbaren Temperaturzonen (3 Zonen am Extruderkopf, 3 Zonen zwischen dem Extruderkopf und der Schlitzdüse und 1 Zone an der Schlitzdüse). Der Einschneckenextruder ist mit einer Schnecke mit einem Durchmesser von 0,5 Zoll (= 1,27 cm) und einem Länge-zu-Durchmesser-Verhältnis von L/D = 24 : 1 ausgerüstet. Das Fassungsvermögen bzw. Schmelzvolumen des Extruders beträgt 15 cm3 und das maximale Kompressionsverhältnis liegt bei 3,4 : 1.These granules were ground to powder in a planetary ball mill under nitrogen flooding, and the powder obtained was dried in a vacuum drying cabinet for 16 hours. The dried powder served as starting material for the production of film using a vertical single-screw Randcastle Microtruder extruder with seven controllable temperature zones (3 zones at the extruder head, 3 zones between the extruder head and the slot die and 1 zone at the slot die). The single screw extruder is equipped with a 0.5 inch (= 1.27 cm) diameter screw with a length to diameter ratio of L/D = 24:1. The capacity or melt volume of the extruder is 15 cm 3 and the maximum compression ratio is 3.4:1.
Das Pulver wurde unter Stickstoffflutung in dem Extrudertrichter vorgelegt. Die Temperaturen in den sieben Extruderzonen betrugen 190 °C in Zone 1, 200 °C in Zone 2, jeweils 210 °C in Zone 3, 4, 5, 6 und 220 °C an der Schlitzdüse. Die Foliendüse wies eine Schlitzbreite 50 mm und eine Schlitzweite 300 µm auf. Der Einschneckenextruder wurde mit einer Schneckendrehzahl von 8 Umdrehungen pro Minute und einem Massedurchsatz von 3,5 g/min betrieben. Die aus der Schlitzdüse austretende Polymerschmelze bzw. -bahn wurde über eine Kühlwalze und eine nachgeordnete Bandabzugseinrichtung mit einer Geschwindigkeit von 0,6 m/min abgezogen. Die Temperatur der Kühlwalze betrug 36 °C. Durch Variation der vorstehenden Prozessparameter konnten Folienbahnen mit einer Breite von 40 bis 50 mm und einer Dicke von 160 bis 240 µm kontinuierlich hergestellt werden. Eine derart erzeugte Folie mit einer Breite von 45 mm und Dicke von 180 µm wies eine Höchstzugkraftdehnung von 448 % sowie eine Zugfestigkeit von 34 N/mm2 auf.The powder was placed in the extruder hopper under a nitrogen purge. The temperatures in the seven extruder zones were 190 °C in
Der elektrische Widerstand der erzeugten Folien in Abhängigkeit von der Temperatur wurde gemäß DIN EN 60093:1993-12 in einer Klimakammer bestimmt. Die Temperatur wurde von 24 °C (Raumtemperatur) in Schritten von 10 °C auf Werte von 30 °C, 40 °C, 50 °C, 60 °C, 70 °C und 80 °C erhöht. An einer Folienprobe mit 180 µm Dicke und einer Fläche von 28,3 cm2 wurden bei 24 °C und 80 °C Widerstandswerte von R(24 °C) = 18,4 mΩ und R(80 °C) = 48,0 mΩ gemessen. Nach Abkühlung der Folie von 80 °C auf 24 °C fiel der Widerstandswert wieder auf seinen Anfangswert. Das Widerstandsverhältnis R(T)/R(24 °C) als Funktion der Temperatur dient als Indikator für die PTC-Intensität und betrug R(T)/R(24 °C) = 2,6.The electrical resistance of the films produced as a function of temperature was determined in accordance with DIN EN 60093:1993-12 in a climatic chamber. The temperature was increased from 24 °C (room temperature) in increments of 10 °C to values of 30 °C, 40 °C, 50 °C, 60 °C, 70 °C and 80 °C. A foil sample with a thickness of 180 µm and an area of 28.3 cm 2 at 24 °C and 80 °C had resistance values of R(24 °C) = 18.4 mΩ and R(80 °C) = 48.0 mΩ measured. After cooling the foil from 80 °C to 24 °C, the resistance value fell back to its initial value. The resistance ratio R(T)/R(24°C) as a function of temperature serves as an indicator for the PTC intensity and was found to be R(T)/R(24°C) = 2.6.
Die physikalischen Eigenschaften des erfindungsgemäßen Formkörpers und des darin enthaltenen Leitfähigkeitsadditivs werden gemäß den folgenden Verfahren gemessen:
In der obenstehenden Tabelle und im Rahmen der vorliegenden Erfindung bezeichnet der Begriff "äquivalenter Durchmesser" den Durchmesser eines "äquivalenten" sphärischen bzw. kugelförmigen Teilchens, welches dieselbe chemische Zusammensetzung und Flächenschnitt (Elektronenmikroskop-Bildgebung) wie das untersuchte Teilchen aufweist. In der Praxis wird der Flächenschnitt jedes untersuchten (irregulär geformten) Teilchens einem sphärischen Teilchen mit einem Durchmesser, der in Einklang mit dem gemessenen Signal steht, zugewiesen.In the above table and in the context of the present invention, the term "equivalent diameter" means the diameter of an "equivalent" spherical particle having the same chemical composition and surface section (electron microscope imaging) as the particle under study. In practice, the surface section of each (irregularly shaped) particle under investigation is assigned to a spherical particle with a diameter consistent with the measured signal.
Die Verteilung von Rußagglomeraten und -aggregaten in den erfindungsgemäßen Formkörpern wird gemäß ASTM D 3849-14a bestimmt. Hierzu wird zunächst ein Volumen von etwa 1 ml des zu untersuchenden Formkörpers in einem geeigneten Lösungsmittel, wie beispielsweise Hexafluorisopropanol, m-Kresol, 2-Chlorphenol, Phenol, Tetrachlorethan, Dichloressigsäure, Dichlormethan oder Butanon aufgelöst. Je nach der Beschaffenheit des Matrixpolymers wird die Lösung bei erhöhter Temperatur und über eine Dauer von bis zu 24 h angesetzt. Die erhaltene polymere Lösung wird mithilfe von Ultraschall in etwa 3 ml Chloroform dispergiert bzw. verdünnt und auf Probengitter für die Analyse mit Rastertransmissionselektronenmikroskop (RTEM) aufgetragen. Die mit dem RTEM erzeugten Bilder der verdünnten polymeren Lösungen werden mit einer Bildanalysesoftware, wie ImageJ ausgewertet, um die Fläche bzw. den äquivalenten Durchmesser der Rußagglomerate und -aggregate zu bestimmen.The distribution of carbon black agglomerates and aggregates in the moldings according to the invention is determined according to ASTM D 3849-14a. For this purpose, a volume of about 1 ml of the shaped body to be examined is first dissolved in a suitable solvent such as hexafluoroisopropanol, m-cresol, 2-chlorophenol, phenol, tetrachloroethane, dichloroacetic acid, dichloromethane or butanone. Depending on the nature of the matrix polymer, the solution is prepared at elevated temperature and for a period of up to 24 hours. The resulting polymeric solution is ultrasonically dispersed or diluted in approximately 3 mL of chloroform and applied to sample grids for scanning transmission electron microscopy (RTEM) analysis. The RTEM generated images of the dilute polymeric solutions are analyzed using image analysis software such as ImageJ to determine the area or equivalent diameter of carbon black agglomerates and aggregates.
Claims (15)
- Electrically conductive moulding with inherent positive temperature coefficient made of a polymer composition which comprises at least one organic matrix polymer (compound material component A), at least one submicro- or nanoscale, electrically conductive additive (compound material component B) and at least one phase-change material with a phase-transition temperature in the range from -42 °C to +150 °C (compound material component D), and the melting range of the polymer composition is within the range from 100 °C to 450 °C, characterized in that the moulding is a monofilament, a multifilament, a fibre or a nonwoven fabric, the phase-change material has been bound into an organic network made of at least one copolymer based on at least two different ethylenic monomers (compound material component C), the copolymer being a block copolymer having at least two different polymer blocks, the phase-change material has been selected in a manner such that the electrical resistivity of the polymer composition increases by at least 50 % for a 60 °C temperature increase within the range from -42 °C to +150 °C, in association with a phase transition of the phase-change material, and the PTC effect results from an increase in the volume of the phase-change material as a consequence of the temperature increase, and when the PTC takes effect the electrically conductive moulding does not experience any changes in the morphology of the crystalline structures of the matrix polymer and does not melt and the mechanical properties of the electrically conductive moulding are not negatively impaired.
- Moulding according to Claim 1, characterized in that the organic matrix polymer (compound material component A) is polyethylene, in particular LDPE, LLDPE or HDPE, an ethylene copolymer, atactic, syndiotactic or isotactic polypropylene, a propylene copolymer, a polyamide, preferably PA 6, PA 11 or PA 12, a copolyamide, preferably PA 6.6, PA 6.66, PA 6.10 or PA 6.12, a homopolyester, an aliphatic, cycloaliphatic or semi-aromatic copolyester, preferably polyethylene terephthalate (PET), polybutylene terephthalate (PBT) or polytrimethylene terephthalate (PTT), a modified polyester, in particular a glycol-modified polyethylene terephthalate (PETG), polyvinylidene fluoride (PVDF), a copolymer having vinylidene fluoride units, a thermoplastic elastomer, a crosslinkable thermoplastic polymer or copolymer, or a mixture or blend of two or more of the polymers mentioned.
- Moulding according to Claim 1 or 2, characterized in that the submicro- or nanoscale, electrically conductive additive (compound material component B) comprises submicro- or nanoscale particles, flakes, needles, tubes, platelets and/or spheroids, in particular submicro- or nanoscale particles made of carbon black, of graphite, of expanded graphite or of graphene; submicro- or nanoscale metal flakes or, respectively, particles, specifically made of Ni, Ag, W, Mo, Au, Pt, Fe, Al, Cu, Ta, Zn, Co, Cr, Ti, Sn or an alloy or mixture thereof; electrically conductive polymers, single- or multiwall, open or closed, unfilled or filled carbon nanotubes (CNT), or metal-filled carbon nanotubes.
- Moulding according to one or more of Claims 1 to 3, characterized in that the organic copolymer based on at least two different ethylenic monomers (compound material component C) is a styrenebutadiene-styrene (SBS) block copolymer, a styrene-isoprene-styrene (SIS) block copolymer, a styrene-ethylene-propylene-styrene (SEPS) block copolymer, a styrene-poly(isoprene-butadiene)-styrene block copolymer or an ethylene-propylene-diene (EPDM) block copolymer; a random or grafted copolymer, in particular an ethylene-vinyl acetate-vinyl alcohol (EVAVOH) copolymer, an ethylene-methyl acrylate-maleic anhydride copolymer, an ethylene-ethyl acrylate-maleic anhydride copolymer, an ethylene-propyl acrylate-maleic anhydride copolymer, an ethylene-butyl acrylate-maleic anhydride copolymer, an ethylene-(methyl, ethyl, propyl or butyl acrylate)-glycidyl methacrylate (EAEGMA) copolymer, an acrylic-butadiene-styrene (ABS) graft copolymer, an ethylene-maleic anhydride (EMSA) copolymer, an ethylene-glycidyl methacrylate (EGMA) copolymer, an ethylene-vinyl acetate (EVA) copolymer, an ethylene-vinyl alcohol (EVOH) copolymer, an ethylene-acrylate (EA) copolymer, specifically an ethylene-(methyl, ethyl, propyl or butyl acrylate) copolymer (EMA, EEA, EPA and, respectively, EBA) or a polyethylene graft copolymer or polypropylene graft copolymer, where the compound material component C optionally additionally comprises amorphous polymers, such as cycloolefin copolymers (COC), polymethyl methacrylates (PMMA), amorphous polypropylene, amorphous polyamide, amorphous polyester or polycarbonates (PC).
- Moulding according to one or more of Claims 1 to 4, characterized in that the phase-change material is a native or synthetic paraffin; a native or synthetic wax, preferably a highly crystalline polyethylene wax; a polyalkylene glycol, preferably polyethylene glycol, a native or synthetic fatty alcohol; a native or synthetic wax alcohol; a polyester alcohol, an ionic liquid or a mixture of two or more of the materials mentioned.
- Moulding according to one or more of Claims 1 to 5, characterized in that the phase-change material has a phase transition in the range from -42 °C to +150 °C, which is associated with a reversible change of its volume.
- Moulding according to one or more of Claims 1 to 6, characterized in that the polymer composition comprises stabilizers, modifiers, dispersing agents and/or processing aids.
- Moulding according to one or more of Claims 1 to 7, characterized in that it comprises from 10 to 90 % by weight of matrix polymer, from 0.1 to 30 % by weight of the electrically conductive additive, from 2 to 50 % by weight of the phase-change material with a phase-transition temperature in the range from -42 °C to 150 °C, from 0 to 10 % by weight of stabilizers, modifiers and dispersing agents, and from 0 to 10 % by weight of processing aids, based in each case on the total weight of the moulding, where the sum of the percentages by weight of the individual constituents is 100 % by weight.
- Moulding according to one or more of Claims 1 to 8, characterized in that the melting point or melting range of the matrix polymer alone or in conjunction with processing aids and/or modifiers is within the range from 100 °C to 450 °C.
- Moulding according to one or more of Claims 1 to 9, characterized in that the melting point or melting range of the phase-change material is below the melting range of the matrix polymer by at least 10 °C, preferably at least 20 °C, particularly preferably at least 30 °C.
- Moulding according to one or more of Claims 1 to 10, characterized in that its resistivity at a temperature of 24 °C is from 0.001 Ω·m to 3.0 Ω·m.
- Moulding according to one or more of Claims 1 to 11, characterized in that in the temperature range 24 °C ≤ T ≤ 90 °C its temperature-dependent resistivity is p(T), where the ratio p(T)/p(24 °C) increases with increasing temperature T from 1 to a value of from 1.1 to 30.
- Moulding according to one or more of Claims 1 to 12, characterized in that in the temperature range 24 °C ≤ T ≤ 90 °C the temperature-dependent resistivity of the moulding is p(T), where the ratio ρ(T)/ρ(24 °C) increases with increasing temperature T from 1 to a value of from 1.1 to 21 and the average value of the increase gradient [ρ(T+ΔT) - p(T)] / [p(24 °C) · ΔT] in the increase range is from 0.1/°C to 3.5/°C.
- Moulding according to one or more of Claims 1 to 13, characterized in that it has been crosslinked with the aid of a chemical crosslinking agent, via heating and/or via treatment with high-energy radiation.
- Process for the production of a moulding according to one or more of Claims 1 to 14, characterized in that the phase-change material (compound material component D) is processed with the copolymer (compound material component C) to give a masterbatch which is then mixed with the other components.
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CN103205056B (en) * | 2012-01-17 | 2016-03-30 | 比亚迪股份有限公司 | A kind of Positive temperature coefficient composite material and a kind of thermistor |
US8558655B1 (en) * | 2012-07-03 | 2013-10-15 | Fuzetec Technology Co., Ltd. | Positive temperature coefficient polymer composition and positive temperature coefficient circuit protection device |
GB201413136D0 (en) * | 2014-07-24 | 2014-09-10 | Lmk Thermosafe Ltd | Conductive polymer composite |
TW201604901A (en) * | 2014-07-30 | 2016-02-01 | 聚鼎科技股份有限公司 | Positive temperature coefficient device |
RU2573594C1 (en) * | 2014-08-07 | 2016-01-20 | Общество с ограниченной ответственностью "Инжиниринговая компания "Теплофон" | Resistive carbon composite material |
US9773589B1 (en) * | 2016-06-24 | 2017-09-26 | Fuzetec Technology Co., Ltd. | PTC circuit protection device |
US10147525B1 (en) * | 2017-12-21 | 2018-12-04 | Fuzetec Technology Co., Ltd. | PTC circuit protection device |
-
2017
- 2017-06-22 US US16/312,147 patent/US10468164B2/en active Active
- 2017-06-22 RU RU2018141551A patent/RU2709631C9/en active
- 2017-06-22 KR KR1020197002181A patent/KR102320339B1/en active IP Right Grant
- 2017-06-22 DE DE102017113884.6A patent/DE102017113884A1/en active Pending
- 2017-06-22 CN CN201780038645.6A patent/CN109328390B/en active Active
- 2017-06-22 MX MX2018015398A patent/MX2018015398A/en unknown
- 2017-06-22 JP JP2018567086A patent/JP7019613B2/en active Active
- 2017-06-22 EP EP17736583.0A patent/EP3475958B1/en active Active
- 2017-06-22 ES ES17736583T patent/ES2938439T3/en active Active
- 2017-06-22 CA CA3029093A patent/CA3029093C/en active Active
- 2017-06-22 WO PCT/EP2017/065461 patent/WO2017220747A1/en unknown
Also Published As
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WO2017220747A1 (en) | 2017-12-28 |
JP7019613B2 (en) | 2022-02-15 |
US20190237224A1 (en) | 2019-08-01 |
RU2709631C1 (en) | 2019-12-19 |
CA3029093C (en) | 2023-08-08 |
JP2019527251A (en) | 2019-09-26 |
DE102017113884A1 (en) | 2017-12-28 |
CN109328390B (en) | 2021-11-05 |
CN109328390A (en) | 2019-02-12 |
ES2938439T3 (en) | 2023-04-11 |
RU2709631C9 (en) | 2020-06-04 |
CA3029093A1 (en) | 2017-12-28 |
KR20190020127A (en) | 2019-02-27 |
MX2018015398A (en) | 2019-04-29 |
KR102320339B1 (en) | 2021-11-03 |
US10468164B2 (en) | 2019-11-05 |
EP3475958A1 (en) | 2019-05-01 |
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