EP2548657A1 - Pièce plastique revêtue et procédé de production de pièce plastique revêtue - Google Patents

Pièce plastique revêtue et procédé de production de pièce plastique revêtue Download PDF

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Publication number
EP2548657A1
EP2548657A1 EP11175089A EP11175089A EP2548657A1 EP 2548657 A1 EP2548657 A1 EP 2548657A1 EP 11175089 A EP11175089 A EP 11175089A EP 11175089 A EP11175089 A EP 11175089A EP 2548657 A1 EP2548657 A1 EP 2548657A1
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EP
European Patent Office
Prior art keywords
graphene
nanographene
plastic part
polymer
composite
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.)
Withdrawn
Application number
EP11175089A
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German (de)
English (en)
Inventor
José Pedro Aguilera Iglesias
Julio Gómez Cordón
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.)
International Automotive Components Group GmbH
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International Automotive Components Group 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 International Automotive Components Group GmbH filed Critical International Automotive Components Group GmbH
Priority to EP11175089A priority Critical patent/EP2548657A1/fr
Publication of EP2548657A1 publication Critical patent/EP2548657A1/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field

Definitions

  • the invention relates to a coated plastic part and a method of producing a coated plastic part wherein the part is intended to be used e.g. in automotive or other industrial equipment, such as a bumper or spoiler of a vehicle or a housing or cover of technical equipment.
  • plastic parts of the vehicle body are advantageous in that they are light weight and do not corrode.
  • Both plastic and metal car body parts are usually coated by a wear-resistant lacquer layer which protect the car body against corrosion and other external influences, such as patrol, acids, mechanical impacts of rocks and the like. The lacquer layer further improves the outer appearance of vehicles.
  • Coated plastic parts are also known from other industrial applications, such as housings and covers for any type of technical equipment.
  • the lacquer coating In the automotive industry, it is common to apply the lacquer coating by an electrostatic wet or powder coating process. When metal parts are used, due to their inherent electric conductivity of the metal parts, the lacquer can be applied directly onto the respective metal parts. This, however, is not possible when parts are made from plastic material.
  • electrostatically coating plastic parts it has been known to first coat the plastic part using a primer having sufficient electric conductivity so that a lacquer layer can be applied in a subsequent electrostatic wet or powder coating process. This requires an additional processing step. Often, a clear finish coat is applied onto the color lacquer. All of this is well known in the art.
  • WO 2010/072592 A1 it is also known to manufacture plastic materials and products for articles in the automotive industry having improved scratch resistance, e.g. for the interior of automobiles, by using a combination of a grafted polymer, such as grafted polyolefine, and a friction reducing agent. These materials are intended to be used without any coating. Besides the automotive industry, the materials are also indicated to be useful in other fields, e.g. for machine housings, appliances, consumer electronic devices.
  • composition comprising carbon black and a polymer of the formula H-[X-R 1 -X-CO-Y-CO] n -OH for forming a powder coated part.
  • the composition is electrically conductive so that it is possible to apply powder by an electrostatic coating process.
  • the coated part can be used as a housing, car body part or the like.
  • EP 0 667 625 describes an electrostatic coated polymer material, including carbon fibers and a metallic powder.
  • WO 2006/025555 A1 describes electrically conductive composites made from a polymer including carbon-based conductive fillers such as carbon black and carbon nanotubes. The parts are finished by an electrostatic coating process.
  • thermoplastic article including a blend of poly(arylen ether) and polyamide, an electrically conductive carbon black, and an impact modifier.
  • the article is coated using an electrostatic powder or wet coating process.
  • WO 2010/102731 A1 describes a form part including a mixture of a thermoplastic polymer and carbon nanotubes for achieving high surface electric conductivity. Also single or multi-layer graphite structures in the form of graphene can be used. The part is used in antistatic or electrically conductive housings for household or electric devices or for components of vehicles which need to have high surface conductivity.
  • the method of the present invention comprises the steps of Forming a composite of a thermoplastic polymer and graphene or nanographene wherein the ratio of polymer and graphene and/or nanographene is chosen in such a way that the composite has low electric resistance. More particularly, the electric conductivity shall be high enough to allow an electrostatic coating process, more particularly an electrostatic wet painting process.
  • the composite is processed in an extruder to produce master-batch pellets or powder and these are processed to mold a plastic part, for example by injection molding or extrusion.
  • the latter step is performed in a manner well known in the art wherein the master-batch pellets and standard polymer or copolymer pellets are mixed and then homogenized and molten in an injection molding tool, for example, to form the final product.
  • a coating is applied directly by an electrostatic coating process, that is without the intermediary of an electrically conductive primer or other intermediary which would support adhesion of the lacquer on the prefabricated plastic part.
  • pellets refers to any particles of processed polymer or polymer composite suitable for use e,g. in an injection molding or extrusion process, without being limited to any particular size or shape of particles.
  • the use of the term “pellets” does not exclude any suitable other form of polymer, such as powder, but shall designate any suitable master-batch in solid form.
  • graphene sheets has been proven to be superior over the previously more commonly used carbon black, carbon fibers and carbon nano-tubes in that it has an extremely high Young modulus of about 1000 Gpa, high electric conductivity in the plane of the graphene sheets of more than 20000 S/cm, high thermal conductivity of more than 5300 W/mK, and an extremely high surface area of approximately 2675 m 2 /g.
  • graphene sheets are easy to functionalize and can disperse in many thermoplastics, resins and solvents.
  • Graphene hence is an ideal supplement for imparting electric conductivity to a plastic part which, in addition, can be manufactured at relatively low costs.
  • a composite of a thermoplastic polymer and graphene or nanographene is hence an ideal raw material for producing plastic parts which are to be coated by an electrostatic coating process, in particular electrostatic wet lacquering, for large-scale production.
  • the thermoplastic polymer for forming the master-batch pellets as well as the polymer or copolymer pellets added in the molding process comprises at least one of a polystyrene, such as acrylonitrile butadiene styrene or acrylester styrol acrylnitril; one of a polyolefin, such as polypropylene or polyethylene; a polyester; or a blend of any of these materials.
  • a polystyrene such as acrylonitrile butadiene styrene or acrylester styrol acrylnitril
  • a polyolefin such as polypropylene or polyethylene
  • a polyester or a blend of any of these materials.
  • the graphene or nanographene is functionalized, for example by attaching chemical bonds and/or by chemical interaction and the composite is prepared in self-assembled monolayers (SAM).
  • SAM self-assembled monolayers
  • the graphene or nanographene comprises layers having an extension of about 200 nm to 30 ⁇ m and a thickness of about 0,3 nm to about 20 nm.
  • the graphene sheets can be broken into smaller parts, warped, folded and/or deformed similar to a very fine piece of gauze.
  • the plastic part is formed by injection molding or extrusion and coated by a wet coating process.
  • single-layer graphene and/or multi-layer graphene can be used wherein the polymer and graphene or nanographene are mixed by an extrusion process.
  • the composite does not include any carbon nanotubes and/or carbon nanofibers and/or carbon fibers and/or carbon black but carbon is present in the composite only in the form of graphene or nanographene.
  • the ratio of polymer and graphene or nanographene is chosen in such a way that the composite of the master-batch and/or pellets or the plastic part has an electric resistivity in the range of 1 M ⁇ /cm to 10 k ⁇ /cm. More particularly, the ratio of polymer and graphene or nanographene can be chosen such that graphene is present in an amount of about 0.1 to 25 wt.% in the master-batch pellets or in the final product.
  • a compatibilizer such as maleic anhydride or aminopropyl silane or stearic acid, can be added to the graphene or nanographene to support blending the graphene sheets into the polymer.
  • the present invention also provides a coated plastic part which comprises an electrically conductive plastic base substrate, the plastic substrate being made from a composite of a thermoplastic polymer and graphene or nanographene, and a coating composition directly apply to the plastic substrate by an electrostatic coating process without the intermediary of an electrically conductive primer.
  • the coated plastic part can have anyone of the properties discussed above in the context of the method of the present invention or any combination of properties discussed above.
  • the coated plastic part is a part of a vehicle or a part of another manufactured equipment, such as a bumper, a spoiler, a housing, or a cover.
  • the process according to a preferred embodiment of the invention is schematically shown in the flow diagram of Fig. 1 .
  • the raw materials for manufacturing the coated plastic part of the present invention are graphene or nanographene and a thermoplastic polymer.
  • the process comprises the steps of preparing functionized nanographene 10 and a polypropylene (PP) base material 20.
  • the materials are mixed in an extruder 30 to form a master batch granulate 32 at the extruder exit.
  • the extruder preferably is a twin screw or planetary extruder which thoroughly mixes and kneads the composite wherein the graphene sheets can be broken, bend, warped and, more generally, deformed so as to intimately mix with the polymer.
  • the masterbatch granulate or pellets and/or powder containing graphene or nanographene are introduced together with standard polymer or copolymer pellets 35 into an injection molding equipment where a plastic part is formed by injection molding 34.
  • the molded plastic part has an electric conductivity sufficiently high to be directly coated in an electrostatic coated process.
  • the ratio of polymer and graphene or nanographene is hence chosen in such a way that the composite or plastic part preferably has an electric resistivity in the range of 1 M ⁇ /cm to 10 k ⁇ /cm.
  • graphene or nanographene can be added to the polymer in an overall amount of 0.1 to 25 wt.-%, preferably 0,5 to 8 wt.-%, depending on the particular polymer material and optional further additives chosen.
  • the above ratio is related to the to the overall quantity of polymer in the final products.
  • the injection molded part is removed from the mold and undergoes a cleaning process 36 as well as a deionization process 38.
  • the cleaned and deionizated plastic part is then introduced into an electrostatic coating system where a base coat is applied by electrostatic painting, preferably electrostatic wet coating 40 using a liquid coating material which is applied directly onto the plastic part.
  • the coated part undergoes polymerization 42, and in a next step 44, an optional clear coating is applied to the plastic part, followed by a further optional step 46 of polymerization.
  • the coated plastic part is then completed.
  • the polymerization serves to "cure" the wet lacquer so that it becomes solid.
  • thermoplastic polymer and graphene allow to omit additional processing steps of flaming and applying an electrically conductive primer to the pre-fabricated plastic part by an aerographic coating process, such as spray coating, so as to allow electrostatic coating of the plastic part.
  • Fig. 2 shows an example of equipment for manufacturing the coated plastic part according to the invention.
  • the process uses functionalized nanographene 50 or graphene and a polymer granulate 52, such as polystyrene, a polyolefin, a polyester, as raw material which are introduced into a twin screw extruder 54 to produce master-batch pellets or powder 56 from the composite.
  • the pellets or powder 56 are then introduced into an injection molding equipment 58 where they are molded together with the standard polymer or copolymer pellets (not shown) to form a pre-fabricated plastic part 60, using a process which, as such, is known in the art.
  • the ratio of nanographene 50 or graphene and the polymer granulate 52 is chosen in such a way that the pre-fabricated plastic part 60 has sufficient conductivity to be directly coatable in an electrostatic coating process.
  • the electric resistivity of the composite of polymer and graphene/nano graphene or the plastic part preferably is in the range of 1 M ⁇ /cm to 10 kn/cm.
  • the pre-fabricated plastic part 60 is introduced into an electrostatic coating equipment (not shown) where wet lacquer is directly applied onto the part by electrostatic coating.
  • a clear coating can be applied onto the coated plastic part.
  • Fig. 3 schematically shows the screw extruder 54 of Fig. 2 , for forming the master-batch pellets or powder of the nanographene/polymer composite.
  • the extruder 54 comprises a main feeder 62 for introducing the polymer and graphene/nanographene which optionally can be compatibilized with some chemical products, such as maleic anhydride or aminopropyl silane or stearic acid. These materials are conveyed and preheated in a first stage 64 of the screw extruder 54 so that the polymer is melted and pre-mixing takes place.
  • a second stage 66 of the twin screw extruder 54 comprises a side feeder 68 where the graphene/nanographene can be added which, however, can be introduced additionally using the main feeder 62. This is designated as "filler" introduction in Fig. 3 .
  • the composition of the polymer, graphene or nanographene, optionally compatibilized, is mixed in the second stage 66 as well as in a third stage 70 and a fourth stage 72 of the screw extruder 54.
  • the third stage 70 comprises a vent opening 74 to the atmosphere and the fourth stage 72 comprises a vacuum vent 76 for venting and degasing the mixture.
  • the screw extruder 54 comprises a metering zone 78 for metering the composite material to produce the master-batch pellets, or powder, or granulate to be used in the subsequent injection molding process.
  • Fig. 4 shows a microscopic photograph of a graphene sheet structure which can be used in the process of the present invention. It can be recognized, that the structures are tissue like.
  • Fig. 5A and 5B show examples of functionalized graphene and nanographene sheets respectively including bonds of additional functional groups, such as OH, EPOXI, COOH, isocyanat, amid, and carbamid.
  • additional functional groups such as OH, EPOXI, COOH, isocyanat, amid, and carbamid.
  • Other materials can be used for functionalizing the graphene sheets, such as silane compounds, phosphonate compounds, sulphur compounds, and organic acid compounds, for example.
  • the coated plastic part according to the present invention can be used in the automotive industry as well in many other industrial applications, such as for bumpers, spoilers, housings, covers and the like.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
EP11175089A 2011-07-22 2011-07-22 Pièce plastique revêtue et procédé de production de pièce plastique revêtue Withdrawn EP2548657A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11175089A EP2548657A1 (fr) 2011-07-22 2011-07-22 Pièce plastique revêtue et procédé de production de pièce plastique revêtue

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP11175089A EP2548657A1 (fr) 2011-07-22 2011-07-22 Pièce plastique revêtue et procédé de production de pièce plastique revêtue

Publications (1)

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EP2548657A1 true EP2548657A1 (fr) 2013-01-23

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107286593A (zh) * 2017-06-13 2017-10-24 浙江金彩新材料有限公司 一种用于聚酯纤维的石墨烯感温变色色母粒及其制备方法
KR20180064827A (ko) * 2016-12-06 2018-06-15 이윤택 그래핀 배리어 코팅 자동차 부품 제조 시스템 및 그의 제조방법
FR3072900A1 (fr) * 2017-10-26 2019-05-03 Compagnie Plastic Omnium Procede de fabrication d’une piece plastique de carrosserie peinte
CN113214729A (zh) * 2020-02-06 2021-08-06 通用汽车环球科技运作有限责任公司 具有改进流动性的模塑涂料
EP3885401A1 (fr) 2020-03-25 2021-09-29 Avanzare Innovacion Tencologica S.L. Matériaux polymères à autodétection résistant aux flammes

Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0576031A1 (fr) 1992-06-26 1993-12-29 Toyota Jidosha Kabushiki Kaisha Méthode de revêtement d'articles en polypropylène
EP0667625A1 (fr) 1994-02-09 1995-08-16 FRISETTA GmbH Matériau en polyamide électrostatique revêtable, son utilisation et méthode pour sa préparation
WO2006025555A1 (fr) 2004-08-31 2006-03-09 Showa Denko K.K. Composites électriquement conducteurs avec résine et vgcf, procédé de fabrication et utilisation de ceux-ci
WO2008019185A1 (fr) 2006-08-07 2008-02-14 Sabic Innovative Plastics Ip B.V. Article fait à partir d'une composition de poly(éther d'arylène)/polyamide
WO2008097343A2 (fr) 2006-08-08 2008-08-14 William Marsh Rice University Matériaux de graphène fonctionnalisé et leur procédé de production
WO2008130431A2 (fr) * 2006-10-06 2008-10-30 The Trustees Of Princeton University Nanocomposites fonctionnels de graphène-polymère pour des applications de barrière aux gaz
DE102007029008A1 (de) * 2007-06-23 2008-12-24 Bayer Materialscience Ag Verfahren zur Herstellung eines leitfähigen Polymerverbundwerkstoffs
DE19854238B4 (de) 1998-11-24 2009-07-09 Granula Polymer Gmbh Verwendung einer Zusammensetzung zur Herstellung von Formteilen
WO2009123771A2 (fr) 2008-02-05 2009-10-08 Crain John M Revêtements contenant des feuilles de graphène fonctionnalisé et articles revêtus par ceux-ci
WO2009134492A2 (fr) 2008-02-05 2009-11-05 Aksay Ilhan A Feuilles de graphène fonctionnalisées ayant des rapports carbone/oxygène élevés
WO2009147415A1 (fr) 2008-06-07 2009-12-10 Hexcel Composites Limited Conductivité améliorée de matériaux en résine et de matériaux composites
DE102008038524A1 (de) 2008-08-20 2010-02-25 Bayer Materialscience Ag Antistatische oder elektrisch leitfähige Polyurethane und ein Verfahren zu deren Herstellung
WO2010072592A1 (fr) 2008-12-22 2010-07-01 Basf Se Procédé d'amélioration de la résistance aux rayures, produits et utilisations associés
WO2010086176A1 (fr) 2009-01-30 2010-08-05 Stichting Dutch Polymer Institute Composition conductrice de polymère
WO2010102731A1 (fr) 2009-03-13 2010-09-16 Bayer Materialscience Ag Corps moulés à partir de mélanges de polymères et de nanoparticules de carbone avec propriété de gradient de la conductibilité électrique
US20100247892A1 (en) 2009-03-31 2010-09-30 Korea Institute Of Science And Technlogy Electroconductive particle and anisotropic conductive film comprising same
EP2266786A1 (fr) 2009-06-23 2010-12-29 GKSS-Forschungszentrum Geesthacht GmbH Fabrication de matières composites à partir de nano-composites
US20110017587A1 (en) 2009-07-27 2011-01-27 Aruna Zhamu Production of chemically functionalized nano graphene materials
US7923491B2 (en) 2008-08-08 2011-04-12 Exxonmobil Chemical Patents Inc. Graphite nanocomposites

Patent Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0576031A1 (fr) 1992-06-26 1993-12-29 Toyota Jidosha Kabushiki Kaisha Méthode de revêtement d'articles en polypropylène
EP0667625A1 (fr) 1994-02-09 1995-08-16 FRISETTA GmbH Matériau en polyamide électrostatique revêtable, son utilisation et méthode pour sa préparation
DE19854238B4 (de) 1998-11-24 2009-07-09 Granula Polymer Gmbh Verwendung einer Zusammensetzung zur Herstellung von Formteilen
WO2006025555A1 (fr) 2004-08-31 2006-03-09 Showa Denko K.K. Composites électriquement conducteurs avec résine et vgcf, procédé de fabrication et utilisation de ceux-ci
WO2008019185A1 (fr) 2006-08-07 2008-02-14 Sabic Innovative Plastics Ip B.V. Article fait à partir d'une composition de poly(éther d'arylène)/polyamide
WO2008097343A2 (fr) 2006-08-08 2008-08-14 William Marsh Rice University Matériaux de graphène fonctionnalisé et leur procédé de production
WO2008130431A2 (fr) * 2006-10-06 2008-10-30 The Trustees Of Princeton University Nanocomposites fonctionnels de graphène-polymère pour des applications de barrière aux gaz
DE102007029008A1 (de) * 2007-06-23 2008-12-24 Bayer Materialscience Ag Verfahren zur Herstellung eines leitfähigen Polymerverbundwerkstoffs
WO2009123771A2 (fr) 2008-02-05 2009-10-08 Crain John M Revêtements contenant des feuilles de graphène fonctionnalisé et articles revêtus par ceux-ci
WO2009134492A2 (fr) 2008-02-05 2009-11-05 Aksay Ilhan A Feuilles de graphène fonctionnalisées ayant des rapports carbone/oxygène élevés
WO2009147415A1 (fr) 2008-06-07 2009-12-10 Hexcel Composites Limited Conductivité améliorée de matériaux en résine et de matériaux composites
US7923491B2 (en) 2008-08-08 2011-04-12 Exxonmobil Chemical Patents Inc. Graphite nanocomposites
DE102008038524A1 (de) 2008-08-20 2010-02-25 Bayer Materialscience Ag Antistatische oder elektrisch leitfähige Polyurethane und ein Verfahren zu deren Herstellung
WO2010072592A1 (fr) 2008-12-22 2010-07-01 Basf Se Procédé d'amélioration de la résistance aux rayures, produits et utilisations associés
WO2010086176A1 (fr) 2009-01-30 2010-08-05 Stichting Dutch Polymer Institute Composition conductrice de polymère
EP2216358A1 (fr) 2009-01-30 2010-08-11 Stichting Dutch Polymer Institute Composition polymère conductrice
WO2010102731A1 (fr) 2009-03-13 2010-09-16 Bayer Materialscience Ag Corps moulés à partir de mélanges de polymères et de nanoparticules de carbone avec propriété de gradient de la conductibilité électrique
US20100247892A1 (en) 2009-03-31 2010-09-30 Korea Institute Of Science And Technlogy Electroconductive particle and anisotropic conductive film comprising same
EP2266786A1 (fr) 2009-06-23 2010-12-29 GKSS-Forschungszentrum Geesthacht GmbH Fabrication de matières composites à partir de nano-composites
US20110017587A1 (en) 2009-07-27 2011-01-27 Aruna Zhamu Production of chemically functionalized nano graphene materials

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180064827A (ko) * 2016-12-06 2018-06-15 이윤택 그래핀 배리어 코팅 자동차 부품 제조 시스템 및 그의 제조방법
KR102588676B1 (ko) 2016-12-06 2023-10-12 이윤택 그래핀 배리어 코팅 자동차 부품 제조 시스템 및 그의 제조방법
CN107286593A (zh) * 2017-06-13 2017-10-24 浙江金彩新材料有限公司 一种用于聚酯纤维的石墨烯感温变色色母粒及其制备方法
FR3072900A1 (fr) * 2017-10-26 2019-05-03 Compagnie Plastic Omnium Procede de fabrication d’une piece plastique de carrosserie peinte
CN113214729A (zh) * 2020-02-06 2021-08-06 通用汽车环球科技运作有限责任公司 具有改进流动性的模塑涂料
US11679532B2 (en) 2020-02-06 2023-06-20 GM Global Technology Operations LLC In-mold coating with improved flowability
EP3885401A1 (fr) 2020-03-25 2021-09-29 Avanzare Innovacion Tencologica S.L. Matériaux polymères à autodétection résistant aux flammes

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