WO2024042075A1 - Mélange de poudres pour un revêtement antiadhésif exempt de téflon - Google Patents

Mélange de poudres pour un revêtement antiadhésif exempt de téflon Download PDF

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Publication number
WO2024042075A1
WO2024042075A1 PCT/EP2023/073027 EP2023073027W WO2024042075A1 WO 2024042075 A1 WO2024042075 A1 WO 2024042075A1 EP 2023073027 W EP2023073027 W EP 2023073027W WO 2024042075 A1 WO2024042075 A1 WO 2024042075A1
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WO
WIPO (PCT)
Prior art keywords
powder mixture
baking
coating
polymer
cooking
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/EP2023/073027
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German (de)
English (en)
Inventor
Christoph Stecher
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.)
ACS Coating Systems GmbH
Original Assignee
ACS Coating Systems 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 ACS Coating Systems GmbH filed Critical ACS Coating Systems GmbH
Priority to JP2025510304A priority Critical patent/JP2025529833A/ja
Priority to EP23762173.5A priority patent/EP4577610A1/fr
Priority to CN202380061341.7A priority patent/CN119855877A/zh
Publication of WO2024042075A1 publication Critical patent/WO2024042075A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes

Definitions

  • the present invention relates to a powder mixture for Teflon-free non-stick coating, a method for coating an object, in particular cooking and baking accessories, using the powder mixture, the use of the Powder mixture for achieving a non-stick and sliding effect on an object, in particular cooking and baking accessories, and an object coated by the process, in particular cooking and baking accessories.
  • the prior art includes PTFE coatings that are usually applied as a triple coating for higher-quality cookware, i.e. in 3 layers with usually at least 2-fold baking.
  • a base layer usually consisting of binding resin dissolved in solvent, for example PAI dissolved in NMP, is wet-sprayed, dried and pre-crosslinked.
  • a transition layer and a top layer are then sprayed wet-on-wet, the top layer essentially containing fluoropolymer, usually PTFE.
  • the entire coating is then baked for approx. 10 minutes at 420°C.
  • These coatings can be modified by pigments and various fillers.
  • the disadvantage is the use of fluoropolymers and the fact that the baking temperature is significantly higher than the decomposition temperature of PTFE, which can result in substances that are harmful to health (PFAS). They also have the disadvantage of releasing toxic substances (PFAS) when used at high temperatures.
  • cooking and baking accessories includes any object that is suitable in shape for holding food and subsequent cooking and baking. Therefore, in addition to pans, the above term also includes baking trays, baking tins, etc., as well as grill trays, grill containers, grill grates, etc.
  • a powder mixture is provided, dry or as a dispersion in a liquid, which comprises powder particles of at least one polyaryl ether ketone (PAEK) polymer and optionally polyphenylene sulfide (PPS) polymer.
  • PAEK polyaryl ether ketone
  • PPS polyphenylene sulfide
  • the powder mixture according to the invention can be produced without adding fluorine or fluorine-containing compounds. This is particularly the case according to the invention when the P2022,2070 WO N August 22, 2023 - 3 - Powder mixture after combustion at 900°C - 1000°C in a moist, oxygen-rich atmosphere does not exceed certain limit values for total fluoride.
  • the powder mixture therefore preferably comprises at most 1000 ppb, preferably at most 100 ppb, particularly preferably at most 25 ppb total fluorides, measured by combustion ion chromatography (TOF-CIC).
  • TOF-CIC combustion ion chromatography
  • samples of the powder mixture are filled into ceramic boats and introduced into an oven where the pyrohydrolysis takes place at 900-1000°C in a moist, O 2 -rich environment. The samples are oxidized under these conditions, the strong carbon-fluorine bond is broken, and the vapors are passed through an absorption solution containing Ar.
  • the powder mixture according to the invention is particularly suitable for coating objects, in particular cooking and baking accessories.
  • the non-stick effect (tested using standard pancakes according to DIN EN 60350-2) of the coating produced using the powder mixture according to the invention met the expectations of a non-stick effect for cookware without the addition of oil and without any fluorine components.
  • the powder mixture preferably comprises at least two polymers, with powder particles comprising the first polymer having a mass-related grain size distribution D50, measured by static image analysis according to ISO 13322-1:2014, which is at most 70 ⁇ m, preferably at most 60 ⁇ m, more preferably at most 50 ⁇ m more preferably at most 40 ⁇ m, in particular at most 30 ⁇ m, and powder particles comprising the second polymer have a mass-related grain size distribution D50, measured by static image analysis according to ISO 13322-1:2014, which is at most 30 ⁇ m, preferably 25 ⁇ m, more preferably at most 20 ⁇ m, even more preferably at most 15 ⁇ m, particularly preferably 10 ⁇ m.
  • This allows the mechanical resistance to be increased.
  • the powder mixture is in the form of a dispersion and preferably the liquid in the dispersion comprises water.
  • the powder mixture preferably comprises at least two PAEK polymers, or at least one PAEK polymer and one PPS polymer, the PAEK polymers preferably from the group consisting of polyetheretherketone (PEEK), polyetherketone (PEK), polyetherketoneketone (PEKK) and polyetherketoneetherketone (PEKKEK), are selected.
  • the polymers preferably have different melting temperatures and/or preferably different melt viscosities.
  • the average melt viscosity of at least one polymer is preferably at most 150 Pa.s, preferably at most 120, more preferably at most 100 Pa.s or particularly preferably at most 90 Pa.s, measured according to ISO 11443 at 400 ° C.
  • the powder mixture preferably also comprises an element from the group consisting of polyamide imides (PAI), polyimides (PI), graphite, MoS 2 and a mixture thereof.
  • PAI polyamide imides
  • PI polyimides
  • MoS 2 metal-oxide-semiconductor
  • the method comprises the following steps: -application of the powder mixture according to the invention to the object, in particular to the cooking and baking accessories, the application preferably being carried out electrostatically, using a vortex sintering process or as a dispersion in liquid, in particular water; -in the case of dispersion, complete removal of the liquid; -Heating the powder mixture to form a polycondensate; and baking the powder mixture above the melting temperature of the polymers.
  • the baking temperature is preferably at most 60 ° C, preferably at most 50 ° C, more preferably at most 40 ° C, even more preferably at most 30 ° C, particularly preferably at most 20 ° C above the liquidus temperature of the polycondensate.
  • the process in particular in the step of heating the powder mixture to form a polycondensate, is carried out without using a fluorosurfactant.
  • the use of the powder mixture for coating objects, in particular cooking and baking accessories to achieve a technical effect, selected from the group consisting of non-stick effect, tested using standard pancakes (DIN EN 60350-2), electrical insulation of at least 1 V, preferably at least 2V, more preferably at least 3V, even more preferably at least 4V, particularly preferably at least 5V, measured in 5% saline solution of the coated inside surface of the object, in particular the cooking and baking accessories, to ensure sufficient Corrosion protection of the metallic substrate of the object, in particular the cooking and baking accessories, and a combination thereof.
  • a technical effect selected from the group consisting of non-stick effect, tested using standard pancakes (DIN EN 60350-2)
  • an object, in particular cooking and baking accessories, which has a coating produced by the method according to the second aspect of the invention is provided.
  • the average thickness of the coating is preferably at most 50 ⁇ m, preferably at most 40 ⁇ m, more preferably at most 25 ⁇ m, particularly preferably at most 25 ⁇ m.
  • Figure 1 shows cooking and baking accessories with an applied dispersion layer in a schematic cross section
  • Figure 2 shows cooking and baking accessories with coating according to the invention
  • Figure 3 shows a process sequence for coating using different process stages
  • Figure 4 shows a flow chart for coating using a dispersion process.
  • An object to be coated or an area of the cooking and baking accessories to be coated represents the substrate SU to be coated.
  • the surface to be coated can first be subjected to a chemical and/or mechanical activation treatment.
  • mechanical roughening for example using a sandblasting blower, or etching with acids, alkalis or plasma or laser treatment can be used.
  • An appropriately pretreated surface has additional chemical/physical bonding points, is clean and grease-free and, in the event of roughening, has a larger surface area, which leads to better adhesion of the coating to be applied.
  • P2022,2070 WO N August 22, 2023 - 9 - A layer DS of a dispersion is then applied to this surface, which, dispersed in a solvent or solvent mixture, contains all components of the coating in a finely divided and as homogeneous particle size distribution as possible.
  • An application method is selected that is suitable for producing a desired layer thickness.
  • the average particle size (D50) of the solids contained in the dispersion corresponds at most to the desired layer thickness for the coating, but is preferably chosen to be smaller.
  • Figure 1 shows a substrate SU coated in this way with an applied dispersion layer DS.
  • a temperature program during which the substrate provided with the dispersion layer DS or the cooking and baking accessories is heated to a temperature above the melting point of the thermoplastic or thermoplastics contained in the dispersion, a homogeneous coating BS is obtained which is pore-free and therefore tight and has good mechanical cohesion and good adhesion to the substrate SU.
  • Figure 2 shows the finished cooking and baking accessories. It is possible to carry out the coating on only a partial area of the surface. The remaining area that is not to be coated can be covered or an application method for the dispersion is chosen that can differentiate between different surface areas, for example brushing or printing.
  • the covering can also be done with a shadow mask while spraying the dispersion.
  • This shadow mask can also be in the form of a film that is applied to the surface of the substrate SU and P2022,2070 WO N August 22, 2023 - 10 - leaves out the areas of the surface to be coated.
  • the film can be removed and, for example, peeled off, with the areas of the dispersion layer DS applied above also being peeled off.
  • Figure 3 shows a variant of the method with which a higher layer thickness can still be achieved despite a smaller particle diameter of the solids contained in the dispersion. For this purpose, after the first dispersion layer DS1 has been applied, as shown in FIG.
  • the solvent is removed; alternatively, the first dispersion layer is also correspondingly pre-compacted by a temperature treatment.
  • the dispersion coating is repeated and a second dispersion layer DS2 is applied. If necessary, this layer can also be pre-compacted and the coating step repeated again.
  • the structure of dispersion layers consisting of several partial layers is brought to a temperature above the melting point of the thermoplastic in a final step, whereby a completely compacted, pore-free closed coating BS is obtained on the substrate SU.
  • a composition suitable for application by means of a dispersion process and which also reduces friction according to the invention contains, for example, solids in the following proportions by weight: 100 percent by weight of PEEK P2022,2070 WO N August 22, 2023 - 11 - Color additives can be added if necessary. It is possible to apply one or more layers.
  • the solids are optionally dispersed with auxiliaries in a solvent, which can be water, or is advantageously miscible or mixed with water, for example alcohol and in particular isopropanol.
  • the dispersion mixture then contains approximately 30 percent by weight of the solids mentioned above.
  • the process sequence just described is shown again more clearly using a flow chart.
  • the method includes, as step 1, producing and preparing the powder mixture.
  • the ingredients which are selected from thermoplastic polymer, filler and dry lubricant, are either brought to a suitable particle size, preferably by grinding and/or by subsequent sorting according to the grain size according to a desired grain size distribution that is as narrow as possible.
  • the solvent is prepared, which is preferably harmless to the environment and health, preferably on an aqueous basis and in particular consists of a mixture of alcohol and water, for example isopropanol and water.
  • An advantageous solvent composition contains, for example, 25 to 75 percent by weight of isopropanol in water. A solvent with approximately 25-50 percent by weight of isopropanol in water is particularly preferred.
  • step 3 the dispersion is produced by adding the solvent to the prepared powder mixture, with a solids content of preferably 20 to 50 P2022,2070 WO N August 22, 2023 - 12 - percent by weight is adhered to.
  • known dispersion aids can be added in small proportions.
  • step 4 the surface of the object is coated, for example by spraying, dipping, brushing, printing or spin-coating. The aim is to achieve a layer thickness of the dispersion layer that is as homogeneous as possible and, if necessary, areas of the surface that are not to be coated are left out of the coating.
  • step 5 the solvent is removed, preferably by evaporation, which can optionally be supported by negative pressure or increased temperature, for example 80 ° C.
  • step 6 the cooking and baking accessories with the applied dried dispersion layer are converted into a homogeneous coating by heating and melting the thermoplastics and then the cooking and baking accessories are cooled again. Following this step 6, a finished coating can be obtained at point 7.
  • a second variant V2 follows step 6, whereby after the first dispersion layer has melted, a new dispersion layer is applied (step 4) and compacted accordingly (steps 5 to 7).
  • a third variant V3 of the method after producing a first coating after step 6, a second second partial layer of the coating, which is different from the first coating, is applied.
  • a further dispersion is produced according to process steps 1 to 3 and the cooking and baking accessories are coated with it according to steps 4 to 6.
  • the method according to variants V1 and V2 can be modified by repeating individual process steps or individual process step sequences in order to achieve a desired layer thickness.
  • a particularly homogeneous coating can be obtained, which makes multiple coating advantageous or necessary due to the small particle diameter.
  • the solid consisted of PEEK from Victrex with an average mass-related grain diameter D50 of 10 ⁇ m and a stated average melt viscosity, measured according to ISO 11443 at 400 ° C, of 150 Pa.s (120 - 180 Pa.s).
  • the substrate in the form of an aluminum pan was cleaned and degreased and then blasted.
  • the Rz after blasting was approx. 20 ⁇ m (measured by scanning or non-contact optical roughness measurement).
  • the aqueous PEEK dispersion was sprayed on using conventional spray guns, dried at approx. 50°C and then baked at an oven temperature of 400°C. This resulted in an optically closed, pore-free surface with a roughness of approx.
  • non-stick effect of the coating produced in this way met the expectations of a non-stick effect for cookware without the addition of oil and without any fluorine components.
  • no fluorosurfactant is required to promote flow.
  • Another advantage is that only one, relatively thin layer is needed to meet all the requirements for a non-stick coating for food contact.
  • wear-resistant PTFE coatings are currently three-layered with a layer thickness of approx. 50 - 60 ⁇ m. With the existing coating of approx. 20 -30 ⁇ m, the use of materials, VOCs and energy can be significantly reduced in addition to the complete avoidance of PFAS. In a further experiment the mechanical resistance should be increased. This could be achieved by adding PEK and/or PEKK.
  • a pan can reach a surface temperature of over 300°C, with the melting temperature of the coating of a reference pan being, for example, 340°C. And not according to the concentration between the two temperatures of 2 polymers involved, but even to that of the higher melting polymer or even higher.
  • a coating according to the invention consisting of PEEK and PEK, did not become liquid up to 400 ° C and above. But even a coating consisting of PEEK and PPS, where the concentration of PPS was 90%, did not become liquid up to 380°C, even though the melting points of the individual polymers are 285 and 340°C.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Cookers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne un mélange de poudres, sec ou sous forme de dispersion dans un liquide, comprenant des particules de poudre d'au moins un polymère de polyaryléthercétone (PAEK) et éventuellement d'un polymère de sulfure de polyphénylène (PPS), la production du mélange de poudres sans ajout de fluor ou de composés contenant du fluor étant possible. Le mélange de poudres comprend préférentiellement au plus 1 000 ppb, préférentiellement au plus 100 ppb, plus préférentiellement au plus 25 ppb de fluorures totaux, mesurés par chromatographie d'échange d'ions à combustion (TOF-CIC). L'invention concerne également un procédé de revêtement d'un objet, en particulier des ustensiles de cuisson et de pâtisserie, à l'aide du mélange de poudres, l'utilisation du mélange de poudres pour assurer un effet technique, choisi parmi un effet antiadhésif et une protection contre la corrosion, et un objet revêtu à l'aide du procédé.
PCT/EP2023/073027 2022-08-23 2023-08-22 Mélange de poudres pour un revêtement antiadhésif exempt de téflon Ceased WO2024042075A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2025510304A JP2025529833A (ja) 2022-08-23 2023-08-22 テフロンフリーノンスティックコーティングのための粉末混合物
EP23762173.5A EP4577610A1 (fr) 2022-08-23 2023-08-22 Mélange de poudres pour un revêtement antiadhésif exempt de téflon
CN202380061341.7A CN119855877A (zh) 2022-08-23 2023-08-22 用于不含特氟龙的不粘涂层的粉末混合物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102022121273.4A DE102022121273A1 (de) 2022-08-23 2022-08-23 Pulvermischung für Teflon freie Antihaftbeschichtung
DE102022121273.4 2022-08-23

Publications (1)

Publication Number Publication Date
WO2024042075A1 true WO2024042075A1 (fr) 2024-02-29

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PCT/EP2023/073027 Ceased WO2024042075A1 (fr) 2022-08-23 2023-08-22 Mélange de poudres pour un revêtement antiadhésif exempt de téflon

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Country Link
EP (1) EP4577610A1 (fr)
JP (1) JP2025529833A (fr)
CN (1) CN119855877A (fr)
DE (1) DE102022121273A1 (fr)
WO (1) WO2024042075A1 (fr)

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EP0343282A2 (fr) * 1988-05-02 1989-11-29 Sekisui Kagaku Kogyo Kabushiki Kaisha Composition de sous-revêtement et substrat métallique revêtu d'une composition de résine
WO2003060012A1 (fr) * 2001-11-22 2003-07-24 HÄRING, Rima Polymeres a chaine principale fonctionnalises
WO2013083693A1 (fr) * 2011-12-06 2013-06-13 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Composites et matières de revêtement contenant des principes actifs inclus dans des enveloppes en matériau biologique
EP3399191A1 (fr) * 2017-05-03 2018-11-07 Kaeser Kompressoren SE Compresseur à vis avec revêtement multi-couche des vis de rotor
DE102019212298A1 (de) * 2019-08-16 2021-02-18 Eos Gmbh Electro Optical Systems Selektives Sintern von polymerbasierten Verbundwerkstoffen

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DE102005009552B4 (de) 2005-03-02 2020-01-23 Acs Coating Systems Gmbh Gegenstand mit reibungsvermindernder Beschichtung und dessen Verwendung sowie Verfahren zur Herstellung einer Beschichtung
JP4825001B2 (ja) * 2005-12-26 2011-11-30 日建塗装工業株式会社 スーパーエンプラ積層膜の溶射成膜法
DE102006061940A1 (de) 2006-12-29 2008-07-03 STE Gesellschaft für Dichtungstechnik mbH Beschichtung mit verbesserten Oberflächeneigenschaften, beschichteter Gegenstand, Verfahren zur Beschichtung und Verwendung
DE102009047865A1 (de) 2009-09-30 2011-03-31 Siemens Aktiengesellschaft Verfahren zum Aufbringen von Kunststoff auf Einzelleiter und HTS-Verbund hergestellt aus den Einzelleitern
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EP2788170B2 (fr) 2011-12-05 2024-11-27 Hexcel Corporation Procédé pour le traitement de paek et d'articles fabriqués à partir de celui-ci
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Publication number Priority date Publication date Assignee Title
EP0343282A2 (fr) * 1988-05-02 1989-11-29 Sekisui Kagaku Kogyo Kabushiki Kaisha Composition de sous-revêtement et substrat métallique revêtu d'une composition de résine
WO2003060012A1 (fr) * 2001-11-22 2003-07-24 HÄRING, Rima Polymeres a chaine principale fonctionnalises
WO2013083693A1 (fr) * 2011-12-06 2013-06-13 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Composites et matières de revêtement contenant des principes actifs inclus dans des enveloppes en matériau biologique
EP3399191A1 (fr) * 2017-05-03 2018-11-07 Kaeser Kompressoren SE Compresseur à vis avec revêtement multi-couche des vis de rotor
DE102019212298A1 (de) * 2019-08-16 2021-02-18 Eos Gmbh Electro Optical Systems Selektives Sintern von polymerbasierten Verbundwerkstoffen

Also Published As

Publication number Publication date
JP2025529833A (ja) 2025-09-09
DE102022121273A1 (de) 2024-02-29
EP4577610A1 (fr) 2025-07-02
CN119855877A (zh) 2025-04-18

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