WO2019063151A1 - 3d printable polymeric composition and products - Google Patents

3d printable polymeric composition and products Download PDF

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Publication number
WO2019063151A1
WO2019063151A1 PCT/EP2018/067763 EP2018067763W WO2019063151A1 WO 2019063151 A1 WO2019063151 A1 WO 2019063151A1 EP 2018067763 W EP2018067763 W EP 2018067763W WO 2019063151 A1 WO2019063151 A1 WO 2019063151A1
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Prior art keywords
particles
printing
composition
composition according
vulcanized rubber
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PCT/EP2018/067763
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German (de)
French (fr)
Inventor
Jens Winkler
Konstantin Efimov
Marco Kormann
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Continental Reifen Deutschland Gmbh
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Publication of WO2019063151A1 publication Critical patent/WO2019063151A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/08—Printing inks based on natural resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing

Definitions

  • the invention relates to compositions based on thermoplastic vulcanizates (TPV), containing a thermoplastic matrix and rubber particles.
  • TPV thermoplastic vulcanizates
  • the invention further relates to the use of the composition in 3D printing processes, to a process for the 3D printing of products containing TPVs according to the invention and to the products produced by this process.
  • thermoplastic polymers have been used for prototyping for quite some time, but a move to mass production or decentralized parts production will become standard in the near future.
  • thermoplastic elastomers are used for 3D printing because these compounds combine thermoplastic and elastomeric properties.
  • TPEs can not fully provide the elastomeric properties of rubber or rubber compounds, particularly adhesion, elastic modulus, abrasion, thermal and mechanical properties, to name but a few.
  • CN 104004377 A discloses a 3D-printable elastomeric compound based on a thermoplastic polyurethane, PLA (polylactic acid) and PHA (polyhydroxybutyric acid), which is processed at a temperature of 240-260 ° C nozzle temperature.
  • PLA polylactic acid
  • PHA polyhydroxybutyric acid
  • the object of the present invention was therefore to provide a composition for use as a tire material, for shoe soles or other products, such as belts or toothed belts, which are suitable for 3D printing and also have rubber-like, elastomeric properties.
  • thermoplastic vulcanizate (TPV) composition comprising up to 70% by weight of a thermoplastic matrix and vulcanized rubber particles, based on 100% by weight of the composition.
  • the composition of the invention has rubber-like properties and is accessible to the 3D printing process.
  • prototypes for tire tread patterns and tire walls can be produced in the field of tire development, which previously had to be laboriously manufactured by Manufaktur.
  • This prototyping is also suitable for the profiles of shoe soles, for example in the field of running shoes or for other components in the automotive sector, for example, for the development of new geometries for timing belts.
  • these products are now also available for series production.
  • thermoplastic matrix comprises thermoplastics selected from acrylonitrile-butadiene-styrene copolymer (ABS), polyamide (PA), polypropylene (PP), polystyrene (PS), polyurethane (PU) or combinations of those mentioned ,
  • rubber particles are to be understood as meaning particles which comprise elastomeric polymers, for example rubber compounds of natural rubber or synthetic rubber.
  • the rubber particles have a spherical or approximately spherical geometry.
  • the rubber particles are vulcanized during the SD printing process and remain as vulcanized rubber particles in the finished product.
  • the rubber particles as well as the vulcanized rubber particles preferably have an average particle size in the range of 1-10 microns, more preferably 2-8 microns.
  • the determination of the average particle size can be determined, for example, by sieve analysis or by laser diffraction, for example with a Malvern Mastersizer 3000®. Preferably, the analysis is carried out by laser diffraction.
  • the average particle size is also retained in the finished product after 3D printing. This can be verified by optical methods in the cross-sectional view or by X-ray methods.
  • the vulcanized rubber particles preferably comprise elastomers, which are preferably selected from natural rubber (NR), synthetic polyisoprene (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR) and nitrile-butadiene rubber (NBR). Likewise, combinations of the elastomers mentioned can be used.
  • the vulcanized rubber particles are preferably included in the range of 1 to 60% by weight in the composition, more preferably 5 to 55% by weight, still more preferably 10 to 50% by weight, and especially 50% by weight, each to 100% by weight of the composition.
  • the composition of the invention may comprise further particles selected from ceramic particles, metallic particles, synthetic diamond-like carbon particles, carbon nanotubes, or the like.
  • the material properties can be selectively influenced, for example with regard to thermal and mechanical stability, abrasion, adhesion hardness, elasticity and the like.
  • the other particles are contained in an amount of preferably 0.1-10% by weight, more preferably 0.1-5% by weight in the composition.
  • the composition may comprise all known additives such as fillers, plasticizers and the like.
  • the further particles are contained either only in the thermoplastic matrix or only in the vulcanized rubber particle component. However, they can also be included in both components. This can be as needed to the desired properties be varied according to the product.
  • the rubber particles and optionally the further particles are preferably located in a filament of the thermoplastic matrix. This has the advantage that during 3D printing during the melting process of the filament, a sufficient temperature is achieved to vulcanize the rubber particles during the 3D printing. This avoids re-vulcanising the printed product and saves costs.
  • Another object of the invention is the use of a composition as described above for use in 3D printing.
  • the 3D printing should include the printing of tire elements, shoe soles or straps, but all other products are also conceivable, which should have corresponding elastomeric properties.
  • sensors can be printed, such as pressure sensors, wear sensors, temperature sensors and the like.
  • Another advantage of the invention is that the 3D printing can be multicolored. As a result, for example, personalized objects can be produced and images, logos or security markings can be incorporated to prevent product piracy.
  • product properties can be adjusted in a targeted manner, for example by local application of reinforcing elements.
  • the invention further relates to a 3D printing method for printing articles containing the TPV composition described above.
  • the method comprises providing a thermoplastic vulcanizate (TPV) as described above and 3D printing the thermoplastic vulcanizate by means of a suitable 3D printer.
  • TPV thermoplastic vulcanizate
  • Suitable 3D printers are for example 3D filament printers, which are known in the art and commercially available.
  • the TPV is provided as a filament.
  • the invention further relates to the products obtained by the process according to the invention.
  • the printed products are preferably tire profiles, tire carcasses, shoe soles or toothed belts.
  • the print pattern is usually computer-aided, for example by CAD, created and transmitted to the 3D printer.
  • the 3D printed products have a ShoreA hardness of 10-150 ShA.
  • Example 1 Production of a 3D Printing Filament
  • the production of a 3D printable filament is carried out by mixing 50% by weight of a thermoplastic and 50% by weight of rubber particles in a twin-screw extruder and extruding the filaments at 180-220 ° C.
  • Table 1 shows the physical properties of the 3D-printable filaments and the measurement methods according to DIN.
  • composition according to the invention the following products were produced in 3D printing:
  • Treads for shoe soles in small numbers were produced in 3D printing for the purpose of testing different materials and sole profiles.
  • an individualized product was produced by adapting the tread hardness to the running weight, to the personal rolling profile as well as to an individual color scheme.
  • the TPV according to the invention has also been tested in mass production as well as for re-soling / repair.
  • composition of the invention was in 3D printing tread in small Quantities produced for the purpose of testing different materials and tread patterns. Further, an individualized tire product has been adapted to the vehicle weight, personal, by adjusting the tread hardness
  • Usage profile (comfort, sport, suspension settings) as well as to the local
  • the TPV according to the invention could be used in 3D printing as repair patches, e.g. with not completely formed sidewall lettering, for the individualization of the
  • Tire sidewall for example, by logos, images and the like can be used successfully.
  • the TPV according to the invention could be used for true-to-life embedding of sensors in the shoe sole or in the tire, e.g. used for temperature and voltage measurements. There is no loss of position due to flow during molding in the vulcanization
  • Metal spikes are produced, which leads to a reduction of material losses compared to injection molding at low volumes of material.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Civil Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Composite Materials (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to compositions on the basis of thermoplastic vulcanizates (TPV) which contain a thermoplastic matrix and rubber particles. The invention further relates to the use of said composition in 3d printing methods, a method for 3D printing products that contain the TPVs according to the invention, and the products produced by said method.

Description

Beschreibung  description
3D-druckbare polymere Zusammensetzung und Erzeugnisse 3D printable polymeric composition and products
Die Erfindung betrifft Zusammensetzungen auf Basis von thermoplastischen Vulkanisaten (TPV), enthaltend eine thermoplastische Matrix und Gummipartikel. Die Erfindung betrifft ferner die Verwendung der Zusammensetzung in 3D-Druckverfahren, ein Verfahren zum 3D-Druck von Erzeugnissen enthaltend erfindungsgemäße TPVs sowie die durch dieses Verfahren hergestellten Erzeugnisse. The invention relates to compositions based on thermoplastic vulcanizates (TPV), containing a thermoplastic matrix and rubber particles. The invention further relates to the use of the composition in 3D printing processes, to a process for the 3D printing of products containing TPVs according to the invention and to the products produced by this process.
3D-Druck wird derzeit in immer mehr technologischen Bereichen eingesetzt. Im Bereich der Kunststoffindustrie werden thermoplastische Polymere bereits seit geraumer Zeit zur Herstellung von Prototypen verwendet, doch eine Entwicklung hin zur Serienproduktion oder auch dezentraler Ersatzteilproduktion wird in naher Zukunft Standard sein. 3D printing is currently being used in more and more technological areas. In the plastics industry, thermoplastic polymers have been used for prototyping for quite some time, but a move to mass production or decentralized parts production will become standard in the near future.
Im Stand der Technik werden thermoplastische Elastomere (TPE) für den 3D-Druck verwendet, da diese Verbindungen thermoplastische und elastomere Eigenschaften vereinen. Allerdings können TPEs nicht in vollem Umfang die elastomeren Eigenschaften von Gummi bzw. Kautschukverbindungen bereitstellen, insbesondere das Haftungsverhalten, das Elastizitätsmodul, Abriebverhalten, thermische und mechanische Eigenschaften, um nur einige zu nennen. In the prior art, thermoplastic elastomers (TPE) are used for 3D printing because these compounds combine thermoplastic and elastomeric properties. However, TPEs can not fully provide the elastomeric properties of rubber or rubber compounds, particularly adhesion, elastic modulus, abrasion, thermal and mechanical properties, to name but a few.
So offenbart die CN 104004377 A eine 3D-druckbare elastomere Verbindung auf Basis eines thermoplastischen Polyurethans, PLA (Polymilchsäure) und PHA (Polyhydroxy- Butyrsäure), welche bei einer Temperatur von 240-260 °C Düsentemperatur verarbeitet wird. Jedoch werden hier keine reinen Gummiverbindungen verarbeitet, da das Temperaturfenster für Gummiverbindungen offensichtlich zu hoch ist. Die Aufgabe der vorliegenden Erfindung bestand deshalb in der Bereitstellung einer Zusammensetzung zur Verwendung als Reifenmaterial, für Schuhsohlen oder anderer Produkte wie Riemen oder Zahnriemen, welche für den 3D-Druck geeignet sind und zudem gummiähnliche, elastomere Eigenschaften aufweisen. Thus, CN 104004377 A discloses a 3D-printable elastomeric compound based on a thermoplastic polyurethane, PLA (polylactic acid) and PHA (polyhydroxybutyric acid), which is processed at a temperature of 240-260 ° C nozzle temperature. However, no pure rubber compounds are processed here, as the temperature window for rubber compounds is obviously too high. The object of the present invention was therefore to provide a composition for use as a tire material, for shoe soles or other products, such as belts or toothed belts, which are suitable for 3D printing and also have rubber-like, elastomeric properties.
Die Aufgabe wurde gelöst durch eine Zusammensetzung auf Basis eines thermoplastischen Vulkanisats (TPV) umfassend bis zu 70 Gew.-% einer thermoplastischen Matrix und vulkanisierte Gummipartikel, bezogen auf 100 Gew.-% der Zusammensetzung. Die erfindungsgemäße Zusammensetzung hat gummiähnliche Eigenschaften und ist dem 3D-Druckverfahren zugänglich. Dadurch können im Bereich der Reifenentwicklung Prototypen für Reifenprofilmuster und Reifenwände erzeugt werden, welche bisher aufwändig durch Manufaktur hergestellt werden mussten. Dieses Prototyping eignet sich ebenso für die Profile von Schuhsohlen, beispielsweise im Bereich Laufschuhe oder aber für andere Komponenten im Automotive Bereich, beispielsweise für die Entwicklung neuer Geometrien für Zahnriemen. Ferner sind diese Produkte mittlerweile auch der Serienproduktion zugänglich. The object has been achieved by a thermoplastic vulcanizate (TPV) composition comprising up to 70% by weight of a thermoplastic matrix and vulcanized rubber particles, based on 100% by weight of the composition. The composition of the invention has rubber-like properties and is accessible to the 3D printing process. As a result, prototypes for tire tread patterns and tire walls can be produced in the field of tire development, which previously had to be laboriously manufactured by Manufaktur. This prototyping is also suitable for the profiles of shoe soles, for example in the field of running shoes or for other components in the automotive sector, for example, for the development of new geometries for timing belts. Furthermore, these products are now also available for series production.
Es hat sich als vorteilhaft erwiesen, wenn die thermoplastische Matrix Thermoplasten, ausgewählt aus Acrylnitril-Butadien-Styrol Copolymer (ABS), Polyamid (PA), Polypropylen (PP), Polystyrol (PS), Polyurethan (PU) oder Kombinationen der genannten, umfasst. It has proved to be advantageous if the thermoplastic matrix comprises thermoplastics selected from acrylonitrile-butadiene-styrene copolymer (ABS), polyamide (PA), polypropylene (PP), polystyrene (PS), polyurethane (PU) or combinations of those mentioned ,
Als Gummipartikel im Sinne dieser Erfindung sind Partikel zu verstehen, die elastomere Polymere umfassen, beispielsweise Kautschukverbindungen aus Naturkautschuk oder Synthesekautschuk. Vorzugsweise weisen die Gummipartikel eine sphärische oder annähernd sphärische Geometrie auf. Die Gummipartikel werden während des SD- Druckverfahrens vulkanisiert und verbleiben als vulkanisierte Gummipartikel im fertigen Erzeugnis. Die Gummipartikel sowie die vulkanisierten Gummipartikel weisen bevorzugt eine mittlere Teilchengröße im Bereich von 1-10 Mikrometer auf, besonders bevorzugt 2-8 Mikrometer. Die Bestimmung der mittleren Teilchengröße kann beispielsweise über eine Siebanalyse ermittelt werden, oder über Laserbeugung, beispielsweise mit einem Malvern Mastersizer 3000®. Bevorzugt erfolgt die Analyse per Laserbeugung. Die mittlere Teilchengröße bleibt nach dem 3D-Druck auch im fertigen Erzeugnis erhalten. Dies kann durch optische Methoden im Schnittbild oder röntgenographische Methoden verifiziert werden. For the purposes of this invention, rubber particles are to be understood as meaning particles which comprise elastomeric polymers, for example rubber compounds of natural rubber or synthetic rubber. Preferably, the rubber particles have a spherical or approximately spherical geometry. The rubber particles are vulcanized during the SD printing process and remain as vulcanized rubber particles in the finished product. The rubber particles as well as the vulcanized rubber particles preferably have an average particle size in the range of 1-10 microns, more preferably 2-8 microns. The determination of the average particle size can be determined, for example, by sieve analysis or by laser diffraction, for example with a Malvern Mastersizer 3000®. Preferably, the analysis is carried out by laser diffraction. The average particle size is also retained in the finished product after 3D printing. This can be verified by optical methods in the cross-sectional view or by X-ray methods.
Die vulkanisierten Gummipartikel weisen vorzugsweise Elastomere auf, welche bevorzugt ausgewählt sind aus Naturkautschuk (NR), synthetischem Polyisopren (IR), Butadien- Kautschuk (BR), Styrol-Butadien- Kautschuk (SBR) und Nitril-Butadien- Kautschuk (NBR). Ebenso sind Kombinationen der genannten Elastomere einsetzbar. Die vulkanisierten Gummipartikel sind bevorzugt im Bereich von 1 bis 60 Gew.-% in der Zusammensetzung enthalten, mehr bevorzugt 5-55 Gew.-%, noch mehr bevorzugt 10-50 Gew-.% und insbesondere 50 Gew.-%, jeweils bezogen auf 100 Gew.% der Zusammensetzung. Die erfindungsgemäße Zusammensetzung kann weitere Partikel, ausgewählt aus keramischen Partikeln, metallischen Partikeln, synthetischen diamantartigen Kohlenstoffpartikeln, Kohlenstoffnanoröhren, oder ähnliche umfassen. Dadurch können die Materialeigenschaften gezielt beeinflusst werden, beispielsweise im Hinblick auf thermische und mechanische Stabilität, Abrieb, Haftung Härte, Elastizität und dergleichen. Die weiteren Partikel sind in einer Menge von vorzugsweise 0,1-10 Gew.-%, mehr bevorzugt 0, 1 -5 Gew.- % in der Zusammensetzung enthalten. Ferner kann die Zusammensetzung alle bekannten Zusatzstoffe wie Füller, Weichmacher und dergleichen umfassen. The vulcanized rubber particles preferably comprise elastomers, which are preferably selected from natural rubber (NR), synthetic polyisoprene (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR) and nitrile-butadiene rubber (NBR). Likewise, combinations of the elastomers mentioned can be used. The vulcanized rubber particles are preferably included in the range of 1 to 60% by weight in the composition, more preferably 5 to 55% by weight, still more preferably 10 to 50% by weight, and especially 50% by weight, each to 100% by weight of the composition. The composition of the invention may comprise further particles selected from ceramic particles, metallic particles, synthetic diamond-like carbon particles, carbon nanotubes, or the like. As a result, the material properties can be selectively influenced, for example with regard to thermal and mechanical stability, abrasion, adhesion hardness, elasticity and the like. The other particles are contained in an amount of preferably 0.1-10% by weight, more preferably 0.1-5% by weight in the composition. Further, the composition may comprise all known additives such as fillers, plasticizers and the like.
Die weiteren Partikel sind entweder nur in der thermoplastischen Matrix oder nur in der vulkanisierten Gummipartikel- Komponente enthalten. Sie können jedoch auch in beiden Komponenten enthalten sein. Dies kann je nach Bedarf an die gewünschten Eigenschaften des Produkts entsprechend variiert werden. Die Gummipartikel und gegebenenfalls die weiteren Partikel befinden sich vorzugsweise in einem Filament der thermoplastischen Matrix. Dies hat den Vorteil, dass beim 3D-Druck beim Schmelzvorgang des Filaments eine ausreichende Temperatur erreicht wird, im die Gummipartikel während des 3D-Drucks zu vulkanisieren. Dadurch kann ein Nach- Vulkanisieren des gedruckten Erzeugnisses vermieden und Kosten eingespart werden. The further particles are contained either only in the thermoplastic matrix or only in the vulcanized rubber particle component. However, they can also be included in both components. This can be as needed to the desired properties be varied according to the product. The rubber particles and optionally the further particles are preferably located in a filament of the thermoplastic matrix. This has the advantage that during 3D printing during the melting process of the filament, a sufficient temperature is achieved to vulcanize the rubber particles during the 3D printing. This avoids re-vulcanising the printed product and saves costs.
Ein weiterer Gegenstand der Erfindung ist die Verwendung einer Zusammensetzung wie oben beschrieben zum Einsatz im 3D-Druck. Another object of the invention is the use of a composition as described above for use in 3D printing.
Vorzugsweise soll der 3D-Druck das Drucken von Reifenelementen, Schuhsohlen oder Riemen umfassen, jedoch sind auch alle anderen Produkte denkbar, die entsprechende elastomere Eigenschaften aufweisen sollen. Ein weiterer Vorteil der erfindungsgemäßen Zusammensetzung liegt darin, dass zusätzlich Sensoren aufgedruckt werden können, beispielsweise Drucksensoren, Verschleiß -Sensoren, Temperatursensoren und dergleichen. Preferably, the 3D printing should include the printing of tire elements, shoe soles or straps, but all other products are also conceivable, which should have corresponding elastomeric properties. Another advantage of the composition of the invention is that in addition sensors can be printed, such as pressure sensors, wear sensors, temperature sensors and the like.
Ein weiterer Vorteil der Erfindung liegt darin, dass der 3D-Druck mehrfarbig erfolgen kann. Dadurch können beispielsweise personalisierte Objekte hergestellt werden und Bilder, Logos oder Sicherheitsmarkierungen zur Verhinderung von Produktpiraterie eingearbeitet werden. Another advantage of the invention is that the 3D printing can be multicolored. As a result, for example, personalized objects can be produced and images, logos or security markings can be incorporated to prevent product piracy.
Durch Variation der Zusammensetzung und der zusätzlichen Partikel können Produkteigenschaften gezielt eingestellt werden, beispielsweise durch lokale Applikation von Verstärkungselementen. By varying the composition and the additional particles, product properties can be adjusted in a targeted manner, for example by local application of reinforcing elements.
Ferner können experimentelle Profilstrukturen für Reifen oder Schuhsohlen bereitgestellt werden oder maßgeschneiderte Profile, die speziell auf den Anwender und dessen Konsumverhalten angepasst sind. Die Erfindung betrifft ferner ein 3D-Druckverfahren zum Drucken von Gegenständen enthaltend die oben beschriebene TPV Zusammensetzung. Furthermore, experimental tread structures for tires or shoe soles can be provided, or tailor made profiles specifically adapted to the user and their consumption behavior. The invention further relates to a 3D printing method for printing articles containing the TPV composition described above.
Das Verfahren umfasst die Bereitstellung eines thermoplastischen Vulkanisats (TPV), wie oben beschrieben, und das 3D-Drucken des thermoplastischen Vulkanisats mittels eines geeigneten 3D-Druckers. The method comprises providing a thermoplastic vulcanizate (TPV) as described above and 3D printing the thermoplastic vulcanizate by means of a suitable 3D printer.
Geeignete 3D-Drucker sind beispielsweise 3D-Filamentdrucker, welche im Stand der Technik bekannt und kommerziell erhältlich sind. Suitable 3D printers are for example 3D filament printers, which are known in the art and commercially available.
Vorteilhafterweise wird das TPV als Filament bereitgestellt. Advantageously, the TPV is provided as a filament.
Die Erfindung betrifft ferner die nach dem erfindungsgemäß hergestellten Verfahren erhaltenen Erzeugnisse. Bevorzugt sind die gedruckten Erzeugnisse Reifenprofile, Reifenkarkassen, Schuhsohlen oder Zahnriemen. The invention further relates to the products obtained by the process according to the invention. The printed products are preferably tire profiles, tire carcasses, shoe soles or toothed belts.
Das Druckmuster wird dabei gewöhnlich computergestützt, beispielsweise durch CAD, erstellt und an den 3D-Drucker übertragen. Die 3D-Druckerzeugnisse weisen eine ShoreA Härte von 10-150 ShA auf. The print pattern is usually computer-aided, for example by CAD, created and transmitted to the 3D printer. The 3D printed products have a ShoreA hardness of 10-150 ShA.
Die Erfindung soll nun anhand einiger Ausführungsbeispiele näher erläutert werden, wobei diese jedoch nicht als limitierend auf den Schutzumfang der Erfindung zu verstehen sind. Beispiele: The invention will now be explained in more detail with reference to some embodiments, but these are not to be understood as limiting the scope of the invention. Examples:
Beispiel 1 : Herstellung eines 3D-Druck-Filaments Example 1: Production of a 3D Printing Filament
Die Herstellung eines 3D-druckbaren Filaments erfolgt durch Mischung von 50 Gew.-% eines Thermoplasten und 50 Gew.-% Gummipartikel in einem Doppelschneckenextruder und extrudieren der Filamente bei 180-220°C. Tabelle 1 zeigt die physikalischen Eigenschaften der 3D-druckbaren Filamente sowie die Messmethoden gemäß DIN. The production of a 3D printable filament is carried out by mixing 50% by weight of a thermoplastic and 50% by weight of rubber particles in a twin-screw extruder and extruding the filaments at 180-220 ° C. Table 1 shows the physical properties of the 3D-printable filaments and the measurement methods according to DIN.
Figure imgf000007_0001
Figure imgf000007_0001
Tabelle 1  Table 1
Mit der erfindungsgemäßen Zusammensetzung wurden die folgenden Erzeugnisse im 3D- Druck hergestellt: With the composition according to the invention, the following products were produced in 3D printing:
1. Schuhsohlen: 1. shoe soles:
Es wurden im 3D-Druck Laufflächen für Schuhsohlen in kleinen Stückzahlen zum Zweck der Erprobung unterschiedlicher Materialien und Sohlenprofile hergestellt. Darüber hinaus wurde ein individualisiertes Produkt durch Anpassung der Laufflächenhärte an das Läuf ergewicht, an das persönliche Abrollprofil sowie eine individuelle Farbgebung hergestellt. Das erfindungsgemäße TPV wurde ferner in der Massenfertigung sowie zur Wiederbesohlung/Reparatur getestet. Treads for shoe soles in small numbers were produced in 3D printing for the purpose of testing different materials and sole profiles. In addition, an individualized product was produced by adapting the tread hardness to the running weight, to the personal rolling profile as well as to an individual color scheme. The TPV according to the invention has also been tested in mass production as well as for re-soling / repair.
2. Reifen Laufstreifen 2. tire treads
Mit der erfindungsgemäßen Zusammensetzung wurde im 3D-Druck Laufstreifen in kleinen Stückzahlen zum Zweck der Erprobung unterschiedlicher Materialien und Laufstreifenprofile hergestellt. Ferner wurde ein individualisiertes Reifenprodukt durch Anpassung der Laufflächenhärte an das Fahrzeuggewicht, an das persönliche With the composition of the invention was in 3D printing tread in small Quantities produced for the purpose of testing different materials and tread patterns. Further, an individualized tire product has been adapted to the vehicle weight, personal, by adjusting the tread hardness
Nutzungsprofil (Komfort, Sport, Fahrwerkseinstellungen) sowie an die lokalen Usage profile (comfort, sport, suspension settings) as well as to the local
Klimaverhältnisse sowie durch eine individuelle Farbgebung hergestellt. Darüber hinaus wurde die Zusammensetzung in der Massenfertigung getestet sowie zur Climate conditions and produced by an individual color. In addition, the composition was tested in mass production as well as
Reparatur/Runderneuerung von Reifen. Repair / retreading of tires.
3. Seitenwände 3. Sidewalls
Das erfindungsgemäße TPV konnte im 3D Druck als Reparaturpatches, z.B. bei nicht vollständig ausgeformter Seitenwandbeschriftung, zur Individualisierung der The TPV according to the invention could be used in 3D printing as repair patches, e.g. with not completely formed sidewall lettering, for the individualization of the
Reifenseitenwand, beispielsweise durch Logos, Bilder und dergleichen erfolgreich eingesetzt werden. Tire sidewall, for example, by logos, images and the like can be used successfully.
4. Sensoren 4. Sensors
Das erfindungsgemäße TPV konnte zum lagegetreuen Einbetten von Sensoren in der Schuhsohle oder im Reifen, z.B. zur Temperatur- und Spannungsmessungen eingesetzt werden. Es resultiert kein Positionsverlust aufgrund von Fließvorgängen beim Einformen in der Vulkanisation The TPV according to the invention could be used for true-to-life embedding of sensors in the shoe sole or in the tire, e.g. used for temperature and voltage measurements. There is no loss of position due to flow during molding in the vulcanization
5. Spikes Mit dem erfindungsgemäßen TPV konnten im 3D-Druck Ummantelungen von 5. Spikes The TPV according to the invention could be used in 3D printing sheaths of
Metallspikes hergestellt werden, wobei es zu einer Verringerung von Materialverlusten gegenüber Spritzguss bei geringen Materialvolumina kommt.  Metal spikes are produced, which leads to a reduction of material losses compared to injection molding at low volumes of material.
Bei allen Bauteilen ist es aufgrund des 3D-Drucks einfach möglich, Bauteileigenschaften lokal an die Beanspruchungen anzupassen, beispielsweise mit einem hohen Gummianteil in den Profilklötzen eines Laufstreifens (Nassgriff) und mit einem hysteresearmen Thermoplast im Profilgrund (Rollwiderstand). Due to 3D printing, it is easily possible to adapt component properties locally to the stresses, for example with a high rubber content, on all components in the tread blocks of a tread (wet grip) and with a low hysteresis thermoplastic in the profile base (rolling resistance).

Claims

Patentansprüche claims
1. Zusammensetzung auf Basis eines thermoplastischen Vulkanisats (TPV) umfassend: 1. A thermoplastic vulcanizate (TPV) based composition comprising:
(a) bis zu 70 Gew.-% einer thermoplastischen Matrix, und (a) up to 70% by weight of a thermoplastic matrix, and
(b) vulkanisierte Gummipartikel (b) vulcanized rubber particles
2. Zusammensetzung nach Anspruch 1, wobei die vulkanisierten Gummipartikel eine Teilchengröße im Bereich 1-10 Mikrometer aufweisen. 2. The composition of claim 1, wherein the vulcanized rubber particles have a particle size in the range 1-10 microns.
3. Zusammensetzung nach einem der Ansprüche 1 oder 2, wobei die thermoplastische Matrix thermoplastische Verbindungen, ausgewählt aus Acrylnitril-Butadien- Styrol Copolymer (ABS), Polyamid (PA), Polypropylen (PP), Polystyrol (PS), Polyurethan (PU) oder Kombinationen der genannten, umfasst. 3. A composition according to any one of claims 1 or 2, wherein the thermoplastic matrix thermoplastic compounds selected from acrylonitrile-butadiene-styrene copolymer (ABS), polyamide (PA), polypropylene (PP), polystyrene (PS), polyurethane (PU) or Combinations of said, covers.
4. Zusammensetzung nach einem der Ansprüche 1 bis 3, wobei die vulkanisierten Gummipartikel ausgewählt sind aus Naturkautschuk (NR), synthetischem Polyisopren (IR), Butadien-Kautschuk (BR), Styrol-Butadien-Kautschuk (SBR) und Nitril-Butadien- Kautschuk (NBR). A composition according to any one of claims 1 to 3, wherein the vulcanized rubber particles are selected from natural rubber (NR), synthetic polyisoprene (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR) and nitrile-butadiene rubber (NBR).
5. Zusammensetzung nach einem der Ansprüche 1 bis 4, wobei die vulkanisierten Gummipartikel im Bereich von 1 bis 60 Gew.-% in der Zusammensetzung enthalten sind. A composition according to any one of claims 1 to 4, wherein the vulcanized rubber particles are included in the composition in the range of 1 to 60% by weight.
6. Zusammensetzung nach einem der Ansprüche 1 bis 5, wobei die Zusammensetzung weitere Partikel, ausgewählt aus keramischen Partikeln, metallischen Partikeln, synthetischen diamantartigen Kohlenstoffpartikeln oder Kohlenstoffnanoröhren, umfasst. A composition according to any one of claims 1 to 5, wherein the composition comprises further particles selected from ceramic particles, metallic particles, synthetic diamond-like carbon particles or carbon nanotubes.
7. Zusammensetzung nach Anspruch 6, wobei die weiteren Partikel nur in der thermoplastischen Matrix oder nur in der vulkanisierten Gummipartikel- Komponente oder in der thermoplastischen Matrix und der vulkanisierten Gummipartikel-Komponente enthalten sind. 7. The composition according to claim 6, wherein the further particles only in the thermoplastic matrix or only in the vulcanized rubber particles Component or in the thermoplastic matrix and the vulcanized rubber particle component are included.
8. Verwendung einer Zusammensetzung nach einem der Ansprüche 1 bis 7 zum SD- Druck. 8. Use of a composition according to any one of claims 1 to 7 for SD printing.
9. Verwendung nach Anspruch 8, wobei der 3D-Druck das Drucken von Reifenelementen, Schuhsohlen oder Riemen umfasst. 9. Use according to claim 8, wherein the 3D printing comprises the printing of tire elements, shoe soles or straps.
10. Verwendung nach Anspruch 8 oder 9, wobei zusätzlich Sensoren aufgedruckt werden. 10. Use according to claim 8 or 9, wherein additionally sensors are printed.
11. Verwendung nach einem der Ansprüche 8-10, wobei der 3D-Druck mehrfarbig erfolgt. 11. Use according to any one of claims 8-10, wherein the 3D printing is multicolored.
12. Verfahren zum Herstellen eines 3D-Druckerzeugnisses, umfassend das 12. A method of producing a 3D printed product, comprising
(a) Bereitstellen einer TPV-Zusammensetzung nach einem der Ansprüche 1 bis 7, (a) providing a TPV composition according to any one of claims 1 to 7,
(b) Drucken des Werkstücks im 3D-Druckverfahren.  (b) Printing the workpiece in the 3D printing process.
13. Verfahren nach Anspruch 12, wobei die TPV-Zusammensetzung als Filament eingesetzt wird. 13. The method of claim 12, wherein the TPV composition is used as a filament.
14. 3D-Druckerzeugnis, hergestellt nach einem Verfahren nach Anspruch 12 oder 13. 14. 3D printed product, produced by a method according to claim 12 or 13.
15. 3D-Druckerzeugnis, enthaltend eine Zusammensetzung nach einem der Ansprüche 1 bis 7. 15. 3D printed product, comprising a composition according to any one of claims 1 to 7.
PCT/EP2018/067763 2017-09-29 2018-07-02 3d printable polymeric composition and products WO2019063151A1 (en)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0404351A2 (en) * 1989-05-26 1990-12-27 Advanced Elastomer Systems, L.P. Dynamically vulcanized alloys having improved stiffness/impact balance
DE102006014985A1 (en) * 2006-03-27 2007-10-04 Deutsche Gumtec Ag Thermoplastic vulcanizate-system based on blend-composition, which is produced by compounding a thermoplastic olefin, in which a portion is used in a chemically modified form, and a chemically modified, finely ground rubber particle
DE102010036122A1 (en) * 2010-09-01 2012-03-01 Nora Systems Gmbh Flooring
CN104004377A (en) 2014-06-10 2014-08-27 广州市傲趣电子科技有限公司 Soft elastic 3D (Three-dimensional) printing rubber consumable material and preparation method thereof
WO2015109141A1 (en) * 2014-01-17 2015-07-23 Lubrizol Advanced Materials, Inc. Methods of using thermoplastic polyurethanes in fused deposition modeling and systems and articles thereof
WO2015195527A1 (en) * 2014-06-16 2015-12-23 Sabic Global Technologies B.V. Process for additive manufacturing using thermoplastic materials having selected melt indexes
CN104761761B (en) * 2015-03-28 2016-08-24 武汉纺织大学 The nanofiber of a kind of high tenacity strengthens rubber-based 3D printing material and preparation method
CN106519379A (en) * 2016-10-31 2017-03-22 四川之江高新材料股份有限公司 Method for preparing graphene/styrene butadiene rubber modified low-density polyethylene used for 3D printing
DE102017200447A1 (en) * 2016-01-19 2017-07-20 Xerox Corporation Conductive polymer composite
CN107118501A (en) * 2017-06-19 2017-09-01 合肥斯科尔智能科技有限公司 A kind of medical corrosion-resistant high tenacity 3D printing material

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0404351A2 (en) * 1989-05-26 1990-12-27 Advanced Elastomer Systems, L.P. Dynamically vulcanized alloys having improved stiffness/impact balance
DE102006014985A1 (en) * 2006-03-27 2007-10-04 Deutsche Gumtec Ag Thermoplastic vulcanizate-system based on blend-composition, which is produced by compounding a thermoplastic olefin, in which a portion is used in a chemically modified form, and a chemically modified, finely ground rubber particle
DE102010036122A1 (en) * 2010-09-01 2012-03-01 Nora Systems Gmbh Flooring
WO2015109141A1 (en) * 2014-01-17 2015-07-23 Lubrizol Advanced Materials, Inc. Methods of using thermoplastic polyurethanes in fused deposition modeling and systems and articles thereof
CN104004377A (en) 2014-06-10 2014-08-27 广州市傲趣电子科技有限公司 Soft elastic 3D (Three-dimensional) printing rubber consumable material and preparation method thereof
WO2015195527A1 (en) * 2014-06-16 2015-12-23 Sabic Global Technologies B.V. Process for additive manufacturing using thermoplastic materials having selected melt indexes
CN104761761B (en) * 2015-03-28 2016-08-24 武汉纺织大学 The nanofiber of a kind of high tenacity strengthens rubber-based 3D printing material and preparation method
DE102017200447A1 (en) * 2016-01-19 2017-07-20 Xerox Corporation Conductive polymer composite
CN106519379A (en) * 2016-10-31 2017-03-22 四川之江高新材料股份有限公司 Method for preparing graphene/styrene butadiene rubber modified low-density polyethylene used for 3D printing
CN107118501A (en) * 2017-06-19 2017-09-01 合肥斯科尔智能科技有限公司 A kind of medical corrosion-resistant high tenacity 3D printing material

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