WO2019063151A1 - Composition polymère pour impression 3d et articles correspondants - Google Patents

Composition polymère pour impression 3d et articles correspondants 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
Authority
WO
WIPO (PCT)
Prior art keywords
particles
printing
composition
composition according
vulcanized rubber
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.)
Ceased
Application number
PCT/EP2018/067763
Other languages
German (de)
English (en)
Inventor
Jens Winkler
Konstantin Efimov
Marco Kormann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Continental Reifen Deutschland GmbH
Original Assignee
Continental Reifen Deutschland GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Continental Reifen Deutschland GmbH filed Critical Continental Reifen Deutschland GmbH
Publication of WO2019063151A1 publication Critical patent/WO2019063151A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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 [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D 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 [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D 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.

Landscapes

  • 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

L'invention concerne des compositions à base de vulcanisats thermoplastiques (TPV), contenant une matrice thermoplastique et des particules de caoutchouc. L'invention concerne en outre l'utilisation de la composition dans des procédés d'impression 3D, un procédé d'impression 3D d'articles contenant des TPV selon l'invention, ainsi que les articles fabriqués par ce procédé.
PCT/EP2018/067763 2017-09-29 2018-07-02 Composition polymère pour impression 3d et articles correspondants Ceased WO2019063151A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102017217399.8 2017-09-29
DE102017217399.8A DE102017217399A1 (de) 2017-09-29 2017-09-29 3D-druckbare polymere Zusammensetzung und Erzeugnisse

Publications (1)

Publication Number Publication Date
WO2019063151A1 true WO2019063151A1 (fr) 2019-04-04

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ID=62846175

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2018/067763 Ceased WO2019063151A1 (fr) 2017-09-29 2018-07-02 Composition polymère pour impression 3d et articles correspondants

Country Status (2)

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DE (1) DE102017217399A1 (fr)
WO (1) WO2019063151A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12371561B2 (en) 2021-04-16 2025-07-29 LCY Chemical Corp. Thermoplastic vulcanizate material, article formed by the same and method for forming the same
US12454097B2 (en) 2021-09-29 2025-10-28 Peridot Print Llc Three-dimensional printing with polyamides and cubic lattice structured particles

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0404351A2 (fr) * 1989-05-26 1990-12-27 Advanced Elastomer Systems, L.P. Mélanges vulcanisés dynamiquement présentant un équilibre entre rigidité et résistance au choc
DE102006014985A1 (de) * 2006-03-27 2007-10-04 Deutsche Gumtec Ag Thermoplastische Vulkanisate
DE102010036122A1 (de) * 2010-09-01 2012-03-01 Nora Systems Gmbh Bodenbelag
CN104004377A (zh) 2014-06-10 2014-08-27 广州市傲趣电子科技有限公司 一种软性弹性3d打印橡胶耗材及其制备方法
WO2015109141A1 (fr) * 2014-01-17 2015-07-23 Lubrizol Advanced Materials, Inc. Procédés d'utilisation de polyuréthanes thermoplastiques dans la modélisation par dépôt fondu, systèmes et articles à base de ceux-ci
WO2015195527A1 (fr) * 2014-06-16 2015-12-23 Sabic Global Technologies B.V. Procédé de fabrication additive à l'aide de matériaux thermoplastiques présentant des indices de fluidité sélectionnés
CN104761761B (zh) * 2015-03-28 2016-08-24 武汉纺织大学 一种高韧性的纳米纤维增强橡胶基3d打印用材料及制备方法
CN106519379A (zh) * 2016-10-31 2017-03-22 四川之江高新材料股份有限公司 3d打印用石墨烯\丁苯橡胶改性低密度聚乙烯的制备法
DE102017200447A1 (de) * 2016-01-19 2017-07-20 Xerox Corporation Leitfähiges Polymerkomposit
CN107118501A (zh) * 2017-06-19 2017-09-01 合肥斯科尔智能科技有限公司 一种医疗用耐腐蚀高韧性3d打印材料

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0404351A2 (fr) * 1989-05-26 1990-12-27 Advanced Elastomer Systems, L.P. Mélanges vulcanisés dynamiquement présentant un équilibre entre rigidité et résistance au choc
DE102006014985A1 (de) * 2006-03-27 2007-10-04 Deutsche Gumtec Ag Thermoplastische Vulkanisate
DE102010036122A1 (de) * 2010-09-01 2012-03-01 Nora Systems Gmbh Bodenbelag
WO2015109141A1 (fr) * 2014-01-17 2015-07-23 Lubrizol Advanced Materials, Inc. Procédés d'utilisation de polyuréthanes thermoplastiques dans la modélisation par dépôt fondu, systèmes et articles à base de ceux-ci
CN104004377A (zh) 2014-06-10 2014-08-27 广州市傲趣电子科技有限公司 一种软性弹性3d打印橡胶耗材及其制备方法
WO2015195527A1 (fr) * 2014-06-16 2015-12-23 Sabic Global Technologies B.V. Procédé de fabrication additive à l'aide de matériaux thermoplastiques présentant des indices de fluidité sélectionnés
CN104761761B (zh) * 2015-03-28 2016-08-24 武汉纺织大学 一种高韧性的纳米纤维增强橡胶基3d打印用材料及制备方法
DE102017200447A1 (de) * 2016-01-19 2017-07-20 Xerox Corporation Leitfähiges Polymerkomposit
CN106519379A (zh) * 2016-10-31 2017-03-22 四川之江高新材料股份有限公司 3d打印用石墨烯\丁苯橡胶改性低密度聚乙烯的制备法
CN107118501A (zh) * 2017-06-19 2017-09-01 合肥斯科尔智能科技有限公司 一种医疗用耐腐蚀高韧性3d打印材料

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12371561B2 (en) 2021-04-16 2025-07-29 LCY Chemical Corp. Thermoplastic vulcanizate material, article formed by the same and method for forming the same
US12454097B2 (en) 2021-09-29 2025-10-28 Peridot Print Llc Three-dimensional printing with polyamides and cubic lattice structured particles

Also Published As

Publication number Publication date
DE102017217399A1 (de) 2019-04-04

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