Non-fluorinated PES-based outer coating

Abstract

The present invention relates to a coated cooking element (1) for a cooking article or electric cooking appliance, comprising a metallic substrate (2) coated on at least one face (2a) by a coating (3) intended to form a cooking face free of fluorocarbon resin and coated on at least the other face (2b) by a coating (4) comprising at least the following layers and in this order from the metallic substrate (2): (4a) primer layer comprising polyethersulfone (PES), (4b) optionally, one or more intermediate layer(s) comprising polyethersulfone (PES) or a mixture of polyethersulfone (PES) and one or more silicone resins, (4c) top layer comprising polyethersulfone (PES) or one or more silicone resins or a mixture of polyethersulfone (PES) and one or more silicone resins.

Description

Title of the invention: Non-fluorinated PES-based exterior coating

[0001] The invention applies in the field of exterior coatings for cooking articles or electrical cooking appliances.

[0002] The present invention addresses the technical problem of improving the thermomechanical properties of an outer coating of a cookware item or an electric cooking appliance. It aims in particular to improve its abrasion resistance and, where applicable, its suitability for stamping. DEFINITIONS

[0003] For the purposes of this invention, the term "layer" should be understood to mean a continuous or discontinuous layer. A continuous layer (also called a monolithic layer) is a single unit forming a flat surface that completely covers the area on which it is laid. A discontinuous layer (or non-monolithic layer) may comprise several parts and is therefore not a single unit.

[0004] The terms "base coat," "primer coat," "bonding coat," or "bonding primer" refer to all the layers from the first coat applied directly to the substrate (it is preferable that this coat adheres well to the substrate and provides all its mechanical properties to the coating: hardness, scratch resistance) to the last layer before the first intermediate or decorative coat. The first layer of the coating is a primer coat.

[0005] The term "intermediate layer" refers to the layers inserted between the primary layer(s) and the finishing layer(s). The intermediate layer(s) may be "decorations" or "decorative layers." The intermediate layer(s) is / are not intended to come into contact with food.

[0006] The term "finish" refers to a continuous surface layer applied after the intermediate layer(s) if the coating comprises one or more intermediate layers, or after the primary layer(s). The final layer of the coating is a finish. Usually, at least the final finish, or even all of the finish layers, is / are transparent to allow visibility of the underlying layers, particularly when the underlying layers are decorative layers. The finish protects the underlying layers from mechanical stress and gives the coating its non-stick properties. Preferably, in the case of a cookware item or electrical cooking appliance, the final finish is intended to come into contact with food.

[0007] The term "decoration" or "decoration layer" means one or more continuous or discontinuous layers comprising a pigment composition. The decoration may be presented in the form of one or more patterns, in one or more colors. A decoration is clearly visible to the user to the naked eye and at a normal operating distance of the cookware or electrical cooking appliance.

[0008] For the purposes of this invention, the term "cooking article" means an object intended for cooking and being heated by an external heating system, such as frying pans, saucepans, sauté pans, woks, or barbecue grills. A cooking article is capable of transferring the heat energy supplied by this external heating system to a material or food in contact with said article.

[0009] For the purposes of this invention, the term "electric cooking appliance" means a heating object having its own heating system, such as an electric crepe maker, an electric raclette appliance, an electric fondue appliance, an electric grill, an electric griddle, an electric cooker, a bread machine, or an electric pressure cooking appliance.

[0010] The term "coating" refers to all the layers adhering to and covering the metallic substrate. The coating obtained according to the invention is advantageously solid; "solid" refers to the characteristic of a cohesive material insoluble in water, in common solvents, and in food components such as aqueous or fatty mixtures, even if the material may exhibit high hardness or high flexibility, such as an elastomer.

[0011] In the present invention, the % by weight are expressed in dry weight, i.e. without solvent. Summary of the invention

[0012] A first object of the invention relates to a coated cooking element (1) for a cooking article or electric cooking appliance, comprising a metallic substrate (2) coated on at least one face (2a) by a coating (3) intended to form a cooking face free of fluorocarbon resin and coated on at least the other face (2b) by a coating (4) comprising at least the following layers and in this order from the metallic substrate (2): - (4a) primer layer comprising polyethersulfone (PES), - (4b) optionally, one or more intermediate layer(s) comprising polyethersulfone (PES) or a mixture of polyethersulfone (PES) and one or more silicone resins, - (4c) topcoat comprising polyethersulfone (PES) or one or several silicone resins or a mixture of polyethersulfone (PES) and one or more silicone resins.

[0013] Another object of the invention relates to a method for manufacturing a cooking article or electric cooking appliance comprising a cooking element coated (1) with a coating (4) according to the invention characterized by the following steps:

[0014] a) a step of supplying a metallic substrate (2) in the form of a substantially flat metallic substrate comprising two opposite faces;

[0015] b) optionally, a treatment step of at least one face (2a) of the metallic substrate (2), to obtain a treated face (2a) promoting the adhesion of a primer layer (4a) on the support (2);

[0016] c) a step of applying layers (4a), optionally (4b), and (4c) of the coating (4);

[0017] d) optionally a drying step between 50°C and 150°C after application of said layers;

[0018] e) a cooking step of the element obtained in step c) or d) at a temperature between 250°C and 420°C.

[0019] f) a step of shaping the element obtained to give it the shape of a support (2) of convex or hollow shape defining an inner face (21) concave and an outer face (22) convex.

[0020] Another object of the invention relates to a cooking article or electric cooking appliance comprising a coated cooking element (1) according to the invention or capable of being obtained according to the process of the invention characterized in that the layer (4c) is intended to be brought into contact with a heating source. FIGURES

[0021] [Fig. 1] ; diagram of a cooking element according to the invention in which the coating (4) comprises a layer (4a), a layer (4b) and a layer (4c)

[0022] [Fig.2] ; diagram of a cooking article according to the invention

[0023] [Fig.3]: Diagram of an electric cooking appliance according to the invention DETAILED DESCRIPTION

[0024] A first object of the invention relates to a coated cooking element (1) for a cooking article or electric cooking appliance, comprising a metallic substrate (2) coated on at least one face (2a) by a coating (3) intended to form a cooking face free of fluorocarbon resin and coated on at least the other face (2b) by a coating (4) comprising at least the following layers and in this order from the metallic substrate (2): - (4a) primer layer comprising polyethersulfone (PES), - (4b) optionally, one or more intermediate layer(s) comprising polyethersulfone (PES) or a mixture of polyethersulfone (PES) and one or more silicone resins, - (4c) topcoat comprising polyethersulfone (PES) or one or several silicone resins or a mixture of polyethersulfone (PES) and one or more silicone resins.

[0025] Advantageously, the layer (4a) is in contact with the metallic substrate (2) by one of its faces by its face (2b).

[0026] The coated face (2a) of the metallic substrate forms a cooking surface. In other words, the coating (3) according to the invention is intended to come into contact with food. The coating (3) can be a non-stick coating of any kind.

[0027] A person skilled in the art will know how to choose the appropriate coating according to the household item and its use(s).

[0028] Advantageously, the coating (3) comprises one or more layers. Typically, the coating (3) comprises, in this order from the substrate (2), one or more primer layers, optionally one or more intermediate layers, and one or more finishing layers.

[0029] The coating (3) does not comprise a fluorocarbon resin, also called a fluorinated polymer or fluoropolymer. In other words, said coating (3) is free of fluorocarbon resin. Thus, the coating (3) does not comprise or emit perfluoroalkyl and polyfluoroalkyl compounds.

[0030] When the coating (3) comprises several layers, they may be identical or different in nature of components, in percentage by weight of components, in thickness, etc.

[0031] The coating (3) may comprise: - one or more additive(s), and / or, - one or more coloring agent(s), and / or - one or more charge(s).

[0032] The coating (3) can be of an organic, inorganic or hybrid nature.

[0033] The other face (2b) of the metallic substrate (2) is coated with the coating (4).

[0034] Advantageously, the thickness of each of the coating layers (4a), optionally (4b) and (4c) is from 5 pm to 15 pm.

[0035] According to one embodiment, at least one intermediate layer (4b) is present in the coating (4) according to the invention. This at least one intermediate layer (4b) is different from at least one primer layer (4a) and at least one topcoat layer (4c). Preferably, in this case, all the intermediate layers (4b) are different from the primer layer(s) (4a) and the topcoat layer(s) (4c). PES

[0036] According to embodiments, the PES content increases from the primer layer (4a) to the finishing layer (4c).

[0037] Thus, in this case, the PES content in the primer layer (4a) is less than the PES content in the layer(s) (4b) when present, which is itself less than the PES content of the finishing layer (4c).

[0038] Thus, advantageously, the PES content of the primary layer (4a) represents from 50% to less than 75% by weight of the primary layer (4a), preferably from 55% to 70%.

[0039] Advantageously, the PES content of the intermediate layer (4b), when present, represents from 75 to less than 85% by weight of the intermediate layer (4b), preferably from 75% to 80%.

[0040] Advantageously, the PES content of the topcoat (4c) represents from 85% to 98% by weight of the topcoat (4c), preferably from 85% to 95%.

[0041] In these embodiments, advantageously, layers (4a), (4b) when present, and (4c) comprise polyethersulfone (PES) and optionally: - one or more thermoplastics other than PES and / or - one or more charge(s) and / or - one or more additive(s), and / or - one or more coloring agent(s).

[0042] In these embodiments, advantageously, the layers (4a), (4b) when present, and (4c) comprise polyethersulfone (PES) and one or more filler(s).

[0043] In these embodiments, advantageously, the filler content decreases from the primer layer (4a) to the finishing layer (4c).

[0044] According to other embodiments, the PES content decreases from the primer layer (4a) to the finishing layer (4c).

[0045] Thus, in this case, the PES content in the primer layer (4a) is greater than the PES content in the layer(s) (4b), when present, which is itself greater than the PES content of the finishing layer (4c).

[0046] Thus, advantageously, the PES content of the primary layer (4a) represents 25% to 30% by weight of the primary layer (4a).

[0047] Advantageously, the PES of the intermediate layer (4b), when present, represents from 20% to less than 25% by weight of the intermediate layer (4b).

[0048] Advantageously, the PES of the topcoat (4c) represents from 10% to less than 20% by weight of the topcoat (4c), preferably from 15% to less than 20%.

[0049] In these embodiments, advantageously, layers (4a), (4b) when present, and (4c) comprise a mixture of polyethersulfone (PES) and one or more silicone resins, and optionally: - one or more thermoplastics other than PES, and / or one or more filler(s) and / or one or more additive(s), and / or one or more coloring agent(s).

[0050] In these embodiments, advantageously, the silicone resin content increases from the primer layer (4a) to the finishing layer (4c).

[0051] In these embodiments, advantageously, the PES content decreases from the primer layer (4a) to the finishing layer (4c) and the silicone content increases from the primer layer (4a) to the finishing layer (4c).

[0052] In these embodiments, advantageously, the (PES+silicone resin) content of the layers (4a), (4b) and (4c) ranges from 40% to 90% or from 50% to 90%, preferably from 60% to 90%, even more preferably from 70% to 90% by weight of each layer.

[0053] In these embodiments, the presence of silicone resins and PES makes it possible to give both the non-stick character of the coating and its suitability for stamping in the case where the coated heating element is shaped after deposition of the coating (4).

[0054] These embodiments are thus particularly suitable in the case of shaping the heating element to give it a convex shape, as for a pan for example.

[0055] According to other embodiments, in particular when the coated heating element is shaped by stamping after deposition of the coating (4) and the coating (4) is subjected to high stresses during this stamping step, the layer (4c) comprises polyethersulfone (PES) and one or more silicone resins and, optionally: one or more thermoplastics other than PES and / or one or more filler(s) and / or; one or more additive(s) and / or; and one or more coloring agent(s).

[0056] the PES content being between 60% and 80% by weight of the layer (4c), the silicone resin content being between 5% and 30% by weight of the layer (4c) and the (PES+silicone resin) content being between 70% and 98%, preferably between 80% and 98%, even more preferably between 90% and 98% by weight of the layer (4c).

[0057] Advantageously, the PES of the primary layer (4a) represents from 50% to less than 75% by weight of the primary layer, preferably from 55% to 70%. Advantageously, the PES of the intermediate layer (4b), when present, represents from 75% to less than 85% by weight of the intermediate layer, preferably from 75% to 80%.

[0058] The high PES content of layer (4c) as well as layers (4a) and (4b) ensures good stamping resistance under high stress. The presence of silicone resin in layer (4c) further guarantees good non-stick properties.

[0059] These embodiments are thus particularly suitable in the case of shaping the heating element to give it a hollow shape for a saucepan for example.

[0060] CHARGES

[0061] Advantageously, the primer layer(s) (4a) and / or the optional intermediate layer(s) (4b) and / or the layer(s) (4c) comprises one or more fillers. According to this embodiment, the primer layer(s) (4a) and / or the optional intermediate layer(s) (4b) and / or the layer(s) (4c) comprises less than 40%, preferably less than 30%, by weight of fillers relative to the total weight of said layer, preferably between 5 and 25% by weight.

[0062] The fillers within the meaning of the invention make it possible to provide mechanical reinforcement and can also provide hydrophobic properties, while improving the mechanical resistance and thermal conductivity of the coating.

[0063] The fillers do not only have the function of adding color to the coating, but can contribute to it.

[0064] Advantageously, the filler(s) is / are chosen from the group consisting of ceramic fillers (SiO2, etc.) and / or mineral and / or metallic fillers (Al2O3, TiO2, etc.) and / or silica and / or diamond particles.

[0065] Preferably, the filler(s) is / are chosen from the group consisting of metal oxides, metal carbides, metal oxynitrides, metal nitrides, and their mixtures.

[0066] Advantageously, said metal is a transition metal, such as at least one of the elements selected from B, Ni, Ti, Zr or Hf.

[0067] Preferably, the charge(s) is / are chosen from the group consisting of:

[0068] - Reinforcement charges: hard organic or inorganic charges; the charges hard inorganic materials are preferably particles of silicon carbide or alumina or zirconia or graphite, or ceramics, or carbonate, or hydrated alumina, aluminum trihydroxide or one or more metal oxide(s), graphite, graphene;

[0069] - other fillers for reinforcement selected from metallic oxides: silica, micas, lamellar charges, clays such as montmorillonite, sepiolite, gypsite, kaolinite and laponite, zinc dioxide, quartz, and zirconium phosphate, alumina, zirconia, zinc oxide, copper oxide, iron oxide;

[0070] - fillers selected from reinforcing fibers: glass or carbon fiber or aramid;

[0071] - conductive charges comprising a transition metal carbide and / or a nitride of transition metal: characterized in that the transition metal is at least one of the elements selected from B, Ni, Ti, Zr or Hf,

[0072] for example: Cubic boron nitride, diamond particles, metallic particles;

[0073] - lamellar charges that can confer lubricating properties, such as by Examples include clays, graphene, and graphite.

[0074] Among the fillers in combination with silicone resins, the preferred fillers are:

[0075] - reinforcing fillers: silica or carbonates with minimum filler content 10-15% / wt and potentially up to 60% / wt,

[0076] - alumina, hydrated alumina, aluminum trihydroxide,

[0077] - silica (precipitated or pyrogenated) with a d50 <0.1 pm and a specific surface BET > 30 m2 / g and preferably between 30 and 500 m2 / g,

[0078] - or a mixture of quartz and silica, diatomaceous earth or crushed quartz, titanium, mica, talc, kaolin, barium sulfate, slaked lime, zinc oxide, expanded vermiculite, non-expanded vermiculite, calcium carbonate etc.

[0079] Preferably, the filler(s) is / are chosen from the group consisting of alumina, silicon carbide, tungsten carbide, boron nitride, quartz, and mixtures thereof.

[0080] Advantageously, the fillers present in the primary layer(s) (4a) or the optional intermediate layer(s) (4b) are hard inorganic fillers, preferably oxides, carbides, metallic nitrides, preferably alumina, silicon carbides or fumed silica.

[0081] Certain hard inorganic fillers such as silicon carbide, in addition to their mechanical reinforcement performance, also have the advantage of being conductive fillers and therefore provide excellent thermal conductivity.

[0082] Adding this type of charge improves the culinary experience with better heat distribution from the metallic substrate to the food in contact with the coating.

[0083] Advantageously, the average diameter d50 of the charges is between 0.1 and 50 pm, advantageously still between 5 and 15 pm.

[0084] Advantageously, the proportion of fillers in a layer is between 0.5 and 30% by dry weight relative to the total weight of said layer after baking, preferably between 5 and 20%.

[0085] Advantageously, the proportion of charges in layer (4a) is greater than 20% by weight, preferably greater than 30% by weight, relative to the total weight of said layer.

[0086] Advantageously, the proportion of charges in the layer (4c) is less than 10% by weight relative to the total weight of said layer.

[0087] Advantageously, the proportion of charges in layers (4a), (4b) and (4c) can be identical or different.

[0088] Advantageously, the nature of the charges in the layers (4a), (4b) and (4c) can be identical or different.

[0089] ADDITIVES

[0090] Advantageously, the primary layer(s) ('a) and / or the intermediate layer(s) (4b) and / or the layer(s) (4c) comprises one or more additives.

[0091] Advantageously, the additive(s) is / are chosen from the group consisting of antifoaming agents, dispersing agents, wetting agents, thickeners, pH adjusters, reactive silicone oils.

[0092] The said antifoaming agent(s) (is) preferably chosen from the group consisting of mineral oils, diols, hydrocarbons, glycerides, oxyrane, emulsified fatty acids.

[0093] The surfactant(s) is / are preferably chosen from the group consisting of glycol ether, ethoxylated alcohol excluding alkyl phenol ethoxylates (APEs), gemini surfactants.

[0094] The dispersing agent(s) is / are preferably chosen from the group consisting of anionic dispersants such as fatty acid derivatives.

[0095] Said thickeners are preferably chosen from the group consisting of acrylic-based or polyurethane-based copolymer, cellulose, fumed silica.

[0096] Said pH adjusters are preferably chosen from the group consisting of Brønsted bases: ammonia, amines (triethylamine, triethanolamine...), hydroxides (sodium hydroxide, potassium hydroxide...), carbonates.

[0097] Advantageously, the primer layer(s) (4a) and the intermediate layer(s) (4b) comprise one or more acrylic resin(s). The acrylic resin(s) is / are advantageously chosen from the group consisting of polymers resulting from an emulsion polymerization of different monomers with other acrylic-based monomers.

[0098] Advantageously, the primary layer(s) (4a) or the intermediate layer(s) (4b) comprises one or more surfactants.

[0099] Advantageously, the primary layer(s) (4a) or the intermediate layer(s) (4b) further comprises one or more antifoaming agents.

[0100] Advantageously, the primary layer(s) (4a) or the optional intermediate layer(s) (4b) further comprises water and / or one or more solvents, preferably unlabeled, for example propionamide, N-formylmorpholine (NFM), N-Methyl Imidazole (NMI), N-Butylpyrrolidone (NBP), dimethyl sulfoxide (DMSO), or alcoholic, for example Propylene Glycol (PPG), Diethylene glycol, dipropylene glycol butyl ether (DPNB).

[0101] Advantageously, the topcoat (4c) comprises a silicone oil. The presence of silicone oil in the topcoat can improve the stretchability of the coating (4) when it is subjected to mechanical stresses, such as during forming by stamping, for example.

[0102] Advantageously, silicone oil represents 1 to 5% by weight of the topcoat (4c), preferably 2% to 4%.

[0103] COLOURING AGENTS

[0104] Advantageously, the primer layer(s) (4a) or the optional intermediate layer(s) (4b) comprises one or more colorant(s). Advantageously, the primer layer(s) (4a) or the optional intermediate layer(s) (4b) comprises less than 30%, preferably less than 20%, by weight of one or more colorant(s) of the total weight of said layer.

[0105] Advantageously, the colouring agent(s) is / are chosen from the group consisting of thermostable pigments, glitter, preferably holographic glitter, and mixtures thereof.

[0106] The proportion of colouring agents in layers (4a), (4b) and (4c) may be between 0.5 and 50% by dry weight relative to the total weight of said layer after baking.

[0107] Advantageously, the proportion of coloring agents in layers (4) and (4b) ranges from 10% to 40% by weight relative to the total weight of said layer.

[0108] Advantageously, the proportion of coloring agents in the layer (4c), when present, is less than 10% by weight relative to the total weight of said layer.

[0109] Advantageously, the proportion of coloring agents in layers (4a), (4b) and (4c) may be the same or different.

[0110] Advantageously, the nature of the coloring agents in layers (4a), (4b) and (4c) may be identical or different.

[0111] Advantageously, layer (4c) is transparent. In this case, if it includes coloring agents, these coloring agents are glitter. Heat-stable pigments

[0112] Preferably, the thermostable pigment(s) is / are chosen from the group consisting of:

[0113] - Titanium rutile-type yellow pigment,

[0114] - Yellow pigment derived from bismuth, for example selected from the vanadates of stabilized bismuth (Py i84)

[0115] - Red pigment, for example selected from perylene red (for example PR149, PR178 and PR224), iron oxide,

[0116] - Orange pigment of the bismuth oxyhalide type (PO85),

[0117] - Bismuth vanadate orange pigment (PO86)

[0118] - Zinc tin titanium orange pigment (PO82)

[0119] - Orange pigment of cerium sulfide (PO75; PO78)

[0120] - Yellow-orange rutile-type pigment of antimony titanium chromium (PBr24)

[0121] - Yellow-orange pigment of the tin and zinc rutile type (Py2i6)

[0122] - Yellow-orange pigment of niobium oxide tin zinc sulfide (Py227)

[0123] - Orange-yellow pigment of double oxides of tin and niobium

[0124] - Co3(PO4)2

[0125] - LiCoPO4

[0126] - CoA12O4

[0127] - Cr2O3

[0128] - TiO2

[0129] - Black pigment PBk28 (Copper chromite black spinel)

[0130] - and their mixtures. Glitter

[0131] The glitter used in the context of the present invention can be independently selected from mica glitter, coated or uncoated, silica glitter, coated or uncoated, aluminum glitter, coated or uncoated, iron oxide glitter, coated or uncoated, or mica or silica glitter coated with titanium dioxide. The glitter used in the context of the present invention can be treated to give a particular color effect.

[0132] Advantageously, the glitter(s) is / are particles selected from the group consisting of mica particles, aluminum particles, mica coated with titanium dioxide or mixtures thereof. Hologram glitter

[0133] Advantageously, the glitter(s) is / are holographic glitter, that is to say a mixture of magnetizable and non-magnetizable particles.

[0134] Magnetizable particles may advantageously be particles comprising at least one ferromagnetic metal. These magnetizable particles may be homogeneous, i.e., made of the same material, or composite, i.e., having a core-shell structure in which the ferromagnetic metal is located in the core and / or the shell of said particles. Examples of composite magnetizable particles include mica flakes coated with iron oxide Fe2O3 or stainless steel fibers coated with a sol-gel material, as corrosion protection during the coating application stages, or plastic material flakes coated with iron oxide Fe2O3, or flakes whose core is made of a ferromagnetic metal and whose shell is made of a plastic material or a sol-gel material.

[0135] According to one embodiment, a portion of said magnetizable particles is oriented so as to form a three-dimensional decoration.

[0136] Advantageously, the mixture of magnetizable and non-magnetizable particles represents between 1% and 5% by weight of the weight of the layer, preferably between 2% and 3% by weight.

[0137] Advantageously, the percentage of non-magnetizable particles in the mixture of magnetizable and non-magnetizable particles is between 15% and 40% by weight relative to the total weight of the mixture of magnetizable and non-magnetizable particles.

[0138] Advantageously, the magnetizable particles have a dimension D50 less than or equal to 23 pm.

[0139] The term “D50” means, in the context of the present invention, the maximum dimension that 50% of the particles have by number.

[0140] Advantageously, the non-magnetizable particles have a D90 dimension between 20% and 250% of the D90 dimension of the magnetizable particles.

[0141] The term “D90” means, in the context of the present invention, the maximum dimension that 90% of the particles have by number.

[0142] Advantageously, the magnetizable particles and / or the non-magnetizable particles are colored on the surface.

[0143] Advantageously, the non-magnetizable particles are made of mica, aluminum, or mica coated with titanium dioxide.

[0144] Advantageously, the magnetizable particles consist of iron, iron oxide, aluminum coated with iron, or mica coated with iron, the iron being in ferritic form.

[0145] THERMOPLASTIC

[0146] Thermoplastics are thermoplastic polymers.

[0147] Advantageously, the thermoplastic polymer(s) other than PES is / are chosen from the group consisting of polyaryletherketone(s) (PAEK), aromatic thermoplastic polymer(s) such as poly(arylethersulfones) (PAES), poly(arylene sulfides) (PAS) or poly(phenylene oxide) (PPO), liquid crystal polymers, heterocyclic thermoplastic polymers and mixtures thereof.

[0148] PAEK

[0149] Advantageously, the polyaryletherketone(s) (PAEK) is / are chosen from the group consisting of: polyetherketones (PEK), polyetheretherketone (PEEK), polyetherketoneketones (PEKK), polyetheretherketoneketones (PEEKK) and polyetherketoneetherketoneketones (PEKEKK), particularly preferably is / are PEEK.

[0150] Other aromatic thermoplastic polymers

[0151] By way of example of aromatic thermoplastic polymer(s), poly(phenylene oxide) (PPO), poly(arylethersulfones) (PAES) polymer, with the exception of polyethersulfone (PES), polyphenylene ether sulfone (PPSU), poly(arylene sulfides) (PAS) and in particular polyphenylene sulfide (PPS), liquid crystal polymers and their mixtures are cited.

[0152] Heterocyclic thermoplastic polymers

[0153] By way of suitable examples of heterocyclic thermoplastic polymers according to the invention are polyetherimides (PEI), polyimides (PI), polyamideimides (PAI) and polybenzymidazole (PBI), or mixtures thereof.

[0154] Advantageously, the thermoplastic polymer(s) is / are selected from the group consisting of polyethersulfone (PES), polyphenylene ether sulfone (PPSU), polyamideimide (PAI), polyimide (PI), poly(phenylene oxide) (PPO), poly(arylene sulfide) (PAS), polyetherimide (PEI), polybenzymidazole (PBI), liquid crystal polymers (LCP), polyphenylene sulfide (PPS), polyarylether ketone (PAEK) including polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ether ketone ketone (PEEKK), polyether ketone ether ketone ketone (PEKEKK) and mixtures thereof.

[0155] Advantageously, the nature of the thermoplastic polymer(s) in layers (4a), (4b) and (4c) may be identical or different.

[0156] SILICONE RESINS

[0157] In the description text, the expression "#silicone resin#" is used interchangeably to refer to silicone before or after crosslinking. In the description text, the term "silicone" designates an organopolysiloxane material. Crosslinking is the step that transforms silicone into an insoluble material, for example by polyaddition, polycondensation. or dehydrogenation. Crosslinking is carried out from precursors which are generally silicone oils or resins, which crosslink to obtain a three-dimensional network forming a material called silicone resin, in the description.

[0158] This crosslinking can be done by thermal activation, or chemical activation using a catalyst, such as platinum.

[0159] Silicone resins can be obtained from precursors, advantageously soluble in a solvent or emulsified in water, such as oils or crosslinkable resins, in particular selected from: a silicone hydride, a silicone oil resin comprising at least one vinyl group (-CH=CH2), a silicone or silicone-polyester resin (copolymer) comprising at least one alkoxy group, for example methoxy or ethoxy, and / or a silicone or silicone-polyester resin (copolymer) comprising at least one alkoxy group, in particular ethoxy, or a hydroxy group and mixtures thereof. These precursors have the ability to crosslink to obtain a silicone resin characterized by its insolubility and substantially solid form.

[0160] Advantageously, these precursors are polymeric or oligomeric, either in the form of silicone oils of varying degrees of branching, or in the form of silicone resins of varying degrees of pre-crosslinking, or copolymers of silicone resins such as silicone-polyester, silicone-alkyd, silicone-polyurethane, or silicone-epoxy resins, or in the form of a mixture of silicone oils, silicone resins, and silicone resin copolymers. The silicon atoms may be substituted by alkyl (in particular methyl) or aryl (in particular phenyl) groups, or mixtures thereof. The oils or resins preferably comprise one or more (2, 3, or more) hydroxy or alkoxy functional groups (in particular methoxy, ethoxy, butoxy) as substituents for the silicon atoms.

[0161] Advantageously, the silicone resin(s), obtained after crosslinking of their precursors, i.e. crosslinked(s), is / are chosen from the group consisting of methyl silicones and / or phenyl silicones and / or methyl-phenyl-silicones, methyl silicone-polyester resin (copolymers), phenyl silicone-polyester resin (copolymers), methyl-phenyl silicones-polyester resin (copolymers), silicone-alkyd resin (copolymers), modified silicone resin and their mixtures.

[0162] Advantageously, the silicone resin(s) is / are chosen from the group consisting of methyl silicones and / or phenyl silicones and / or methyl-phenyl-silicones, methyl silicone-polyester resin (copolymers), phenyl silicone-polyester resin (copolymers), methyl-phenyl silicones-polyester resin (copolymers), silicone-alkyd resin (copolymers), modified silicone resin and mixtures thereof.

[0163] Silicone resins can be obtained from precursors, in particular selected from: a silicone hydride, a silicone resin comprising at least one vinyl group (-CH=CH2), a silicone-polyester resin (copolymer) comprising at least one methoxy group, and / or a silicone-polyester resin (copolymer) comprising at least one ethoxy group, and mixtures thereof.

[0164] The silicone resin forms a network which may consist of a combination of 4 simple organosiloxane units designated M, D, T and Q depending on the degree of substitution by the oxygen of the silicon atom, as described in the following table, where R is an organic substituent described later.

[0165] [Tables 1] Structure Degree of Substitution Symbol by foxygen | 1 1 y R <' ' r.; ■ O— R 2 | D $ ô 3 T 4 | Q

[0166] The organopolysiloxane material or polymer is obtained by crosslinking from precursors that may be monomeric or polymeric, or, intermediately, oligomeric. The organopolysiloxane polymer may also be obtained from a mixture of these different types of precursors. When the network contains a higher number of T and Q units than D units, the crosslinking density is higher. The distribution among the M, D, T, and Q units depends on the chemical structure of the precursors, in particular on this M, D, T, and Q distribution within the precursors.

[0167] The polymeric precursors are organopolysiloxanes. These macromolecules are formed of M, D, T, and / or Q units as described in the table, where R is independently an alkyl group, in particular methyl, or aryl group, in particular phenyl, different natures of R being able to be present on the same macromolecule.

[0168] Organopolysiloxanes can be either linear or sparsely branched (predominantly D groups), or branched or highly branched (predominantly T and Q groups). Linear or sparsely branched organopolysiloxanes are generally liquid, more or less viscous at room temperature, and are called silicone oils. Branched or highly branched (pre-crosslinked) organopolysiloxanes form a network at the scale of the individual macromolecule and are called silicone resins. At room temperature, the resins are substantially in solid form, or in the form They can be liquid, provided in particular that they have a sufficiently low molecular weight, in the form of a solution in a solvent or as an aqueous emulsion. They can be copolymerized with organic polymers or oligomers not containing silicon, chosen in particular from polyesters, acrylics, alkyds, polyurethanes, and epoxy resins.

[0169] When the crosslinking is a hydrolysis-polycondensation: it is carried out by means of the reactive hydroxy or alkoxy functions, in particular methoxy, ethoxy or butoxy, present on the organopolysiloxane.

[0170] When the crosslinking is a polyaddition (or hydrosilylation): it takes place by reaction between the reactive vinyl functions (-CH=CH2) present on one of the organopolysiloxanes and the reactive silyl hydride functions (Si-H) present on the other organopolysiloxane mixed with the first.

[0171] All these reactive functions are present on each organopolysiloxane, with at least one present and two, three, or more present... as much as the molecular structure allows. Silicone oils containing at least one reactive function are called "reactive oils." The reactive functions can be located either at the end of the macromolecular chain (termination) or distributed along the chain.

[0172] Silicone-polyester resins in particular have silicone / polyester mass ratios for example 90 / 10, 80 / 20, 70 / 30, 60 / 40, 50 / 50, 40 / 50, 30 / 70, 20 / 80, 10 / 90, advantageously between 80 / 20 and 50 / 50.

[0173] Linear PDMS silicone oils, pure or pre-emulsified in water, are characterized first by their molecular weight, which is directly proportional to the viscosity of the pure oil. They are then characterized by the presence or absence of reactive functional groups, for example hydroxyl groups on the silicon atoms (silanol), their number, and their location on the molecular chain. For example, reactive oils with viscosities between 50 and 20,000 mPa·s, and in particular between 300 and 5,000 mPa·s, can be used, possessing at least one reactive functional group, preferably at least two, which can be located at the end of the chain.

[0174] Polymeric precursors reacting by polyaddition may include, for example, polymethylhydrosiloxane, vinylmethylsiloxane, vinyl-terminated polydimethylsiloxane (PDMS), in particular linear, vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymers, hydride-terminated polydimethylsiloxanes, hydride-terminated polyphenylmethylsiloxanes, cyclic vinylmethylsiloxane, vinyl-MQ resin, trimethylsilyl-terminated polymethylhydrosiloxane, trimethylhydrosiloxane-terminated dimethylsiloxane copolymer, MQ resin hydride, and the like, and combinations thereof.

[0175] Polymeric precursors reacting by hydrolysis-polycondensation, whether silicone resins or silicone oils, may include, for example, poly(methylsilsesquioxanes), poly(propylsilsesquioxanes), poly(phenylsilsesquioxanes), polydimethylsiloxane (PDMS), polydimethylsiloxane (PDMS), terminated trimethylsilyl, polydimethylsiloxane (PDMS) terminated hydroxyl, polydimethylsiloxane (PDMS) terminated silanol, polyphenylsiloxane (PDMS) terminated silanol, diphenylsiloxane-dimethylsiloxane copolymer terminated silanol, poly(2-acetoxyethylsilsesquioxanes), organo-modified alkoxysilanes and their oligomers, and all similar macromolecules and mixtures thereof.

[0176] The organopolysiloxane material or polymer can also be obtained by crosslinking a mixture of one or more monomeric precursors and one or more polymeric precursors as described above, as well as one or more oligomeric precursors, which may be linear, branched, or cyclic. These oligomeric precursors have a lower molecular weight than the polymeric precursors. Polymeric and / or oligomeric precursors having more than two reactive functions as described above, advantageously much more than two, can be added to the mixture as a "co-binder" to promote a high crosslinking density of the organopolysiloxane polymer ultimately obtained.

[0177] Monomeric, oligomeric and / or polymeric precursors, in particular silicone resins, copolymerized or not with an organic polymer, play the role of polymeric binder in order to obtain the solid organopolysiloxane polymer combined with the thermoplastics of each layer.

[0178] Silicone oil-type organopolysiloxane precursors can be considered as additives if they are added in small quantities (generally between 0.1 and 5% dry) to the overall formula of a layer, independently of the other components for the formation of the solid organopolysiloxane polymer.

[0179] Crosslinking may require a catalyst:

[0180] - In the case of the crosslinking of organopolysiloxanes by hydrolysis- polycondensation, the formula may include a metallic catalyst, such as for example platinum-based, tin-based, zinc-based, zirconium-based and cerium-based metal complexes, in particular platinum-cyclovinylmethyl-silxane complexes, tin ethylhexanoate, zinc ethylhexanoate, zirconium ethylhexanoate, cerium ethylhexanoate, and tin dibutyl laurate.

[0181] - In the case of the crosslinking of organopolysiloxanes by hydrosylation, the addition a catalyst may be required: this could be for example platinum or a suitable platinum-based catalyst such as the Karstedt catalyst or the Ashbys catalyst.

[0182] A crosslinking agent, for example carrying Si-H bonds, may be present.

[0183] OTHER ARCHITECTURES

[0184] Preferably, the intermediate layer(s) (4b) only partially cover the base layer (4a).

[0185] According to one embodiment, the topcoat (4c) consists of one or more silicone resins, and optionally: - of one or more charge(s) and / or - of one or more additive(s), and / or - of one or more coloring agent(s).

[0186] According to one embodiment, layer (4c) is made up of:

[0187] - of a silicone elastomer obtained from at least one organopolysiloxane carrier of vinyl reactive functions (-CH=CH2), at least one other organopolysiloxane bearing silyl hydride (Si-H) reactive functions, preferably in the presence of a metallic catalyst; and possibly:

[0188] - of one or more thermoplastics

[0189] - of one or more charge(s), and / or

[0190] - of one or more additive(s), and / or

[0191] - of one or more coloring agents.

[0192] when at least one layer (4b) is present.

[0193] In this case, advantageously, the PES content increases from layer (4a) to layer (4b). Layer (4a) and layer (4b) can be as described above.

[0194] Organopolysiloxanes bearing reactive (4c) layer functions are precursors that react by crosslinking, which is a polyaddition (or hydrosilylation). This crosslinking occurs through a reaction between the reactive vinyl (-CH=CH2) functions present on one of the organopolysiloxanes and the reactive silyl hydride (Si-H) functions present on the other organopolysiloxane mixed with the first.

[0195] This crosslinking can be done by thermal activation, or chemical activation using a catalyst.

[0196] Advantageously, organopolysiloxanes bearing reactive functions of the (4c) layer are silicone oils.

[0197] Reactive functional groups are present on each organopolysiloxane, with at least one and two, three, or more possible, as far as the molecular structure allows. Silicone oils containing at least one reactive functional group are called "reactive oils." The reactive functional groups may be located either at the end of the macromolecular chain (termination) or distributed along the chain.

[0198] The addition of a catalyst may be necessary for crosslinking: this may be, for example, platinum or a suitable platinum-based catalyst such as the Karstedt catalyst or the Ashbys catalyst.

[0199] The thermoplastics, additives and coloring agents are as described above. The thermoplastic of layer (4c) may also be PES.

[0200] Advantageously, the thickness of the topcoat (4c) is from 0.1 pm to 10 pm, preferably from 0.5 pm to 5 pm, particularly preferably from 1 pm to 2 pm.

[0201] METALLIC SUBSTRATE

[0202] Advantageously, said metallic substrate (2), also called support, is a substrate of aluminum, stainless steel, cast iron or aluminum, iron, titanium or copper.

[0203] For the purposes of this invention, aluminium means a metal consisting of 100% aluminium or an aluminium alloy.

[0204] Advantageously, the metallic substrate (2) is an aluminum substrate, a stainless steel substrate, or a multilayer metallic substrate. The metallic substrate (2) may be a two-layer or three-layer substrate, these multilayers being obtained, for example, by co-lamination, by hot diffusion under load (solid state bonding), or by hot or cold impact bonding.

[0205] Preferably, the metallic substrate (2) comprises an alternation of layers of metal and / or metallic alloy.

[0206] According to one embodiment, the metallic substrate (2) is an aluminum alloy substrate, a stainless steel substrate or a multilayer metallic substrate whose face (2a) is made of aluminum alloy or stainless steel.

[0207] Preferably, the metallic substrate (2) is an aluminum substrate.

[0208] Advantageously, the thickness of the metallic substrate (2) is between 0.5 mm and 10 mm.

[0209] Advantageously, the face (2a) of the metallic substrate (2) has previously undergone a surface treatment to improve the adhesion of the coating to said substrate.

[0210] According to one embodiment, the surface of the face (2a) of the metallic substrate (2) has undergone a surface treatment, said surface treatment being a chemical attack, a brushing, a hydration, a sandblasting, a shot blasting, a physicochemical treatment of the plasma or corona or laser type, a chemical activation or a combination of these different techniques.

[0211] Advantageously, the surface of the substrate (2a) onto which the coating (3) according to the invention is to be applied can be treated so as to increase its specific surface area; for an aluminum substrate, this treatment can be carried out by anodizing (creation of a tubular alumina structure), by chemical etching, by sandblasting, by brushing, by Shot blasting or material addition using a technology such as thermal spraying (flame, plasma, or arc spray). Other metallic substrates can also be polished, sandblasted, brushed, micro-blasted, or have material added using a technology such as thermal spraying (flame, plasma, or arc spray).

[0212] As examples of metallic substrates that can be used in the present invention, advantageous examples include substrates made of anodized or unanodized aluminum, optionally polished, brushed, sandblasted, shot-blasted or micro-beaded; substrates made of anodized or unanodized aluminum alloy, optionally polished, brushed, sandblasted or micro-beaded; substrates made of steel, optionally polished, brushed, sandblasted, shot-blasted or micro-beaded; substrates made of stainless steel, optionally polished, brushed, sandblasted or micro-beaded; substrates made of cast steel, aluminum or iron; and substrates made of copper, optionally hammered or polished.

[0213] Advantageously, the substrate can be selected from substrates comprising ferritic stainless steel / aluminum / austenitic stainless steel layers, substrates comprising stainless steel / aluminum / copper / aluminum / austenitic stainless steel layers, cast aluminum caps, aluminum or aluminum alloy caps lined with an outer stainless steel base, metallic co-laminated substrates, for example two-layer co-laminated substrates comprising a stainless steel layer (for example intended to form the inner face of the article) and an aluminum or aluminum alloy layer, anodized or not (for example intended to form the outer face of the article).

[0214] Advantageously, the mean arithmetic roughness Ra of the surface of the face (2a) of the metallic substrate (2) is greater than or equal to 1 pm.

[0215] The arithmetic mean roughness Ra is measured using a roughness tester according to ISO 4287. Ra represents the arithmetic mean of the deviations from the mean. Surface topography can be studied, in particular, with a profilometer with a probe equipped with a fine stylus fitted with a diamond tip, or with an optical metrology device such as Altisurf®, in which a chromatic confocal sensor allows for non-contact measurement. The study of this surface topography makes it possible to define the arithmetic mean roughness Ra.

[0216] PROCESS

[0217] The invention also relates to a method for manufacturing a cooking element coated (1) with a coating (4) for a household article according to the invention, characterized by the following steps:

[0218] a) a step of supplying a metallic substrate (2) comprising two opposite faces;

[0219] b) optionally, a treatment step of at least one face (2a) of the metallic substrate (2), to obtain a treated face (2a) promoting the adhesion of a primer layer (4a) to the support (2);

[0220] c) a step of applying layers (4a), optionally (4b) and (4c) of the coating (4);

[0221] d) optionally a drying step between 50°C and 100°C after application of said layers;

[0222] e) a cooking step of the element obtained in step c) or d) at a temperature between 250°C and 400°C

[0223] The invention also relates to a method for manufacturing a cooking article or electric cooking appliance comprising a heating element coated (1) with a coating (4) according to the invention characterized by the following steps:

[0224] a) a step of supplying a metallic substrate (2) in the form of a substantially flat metallic substrate comprising two opposite faces;

[0225] b) optionally, a treatment step of at least one face (2a) of the metallic substrate (2), to obtain a treated face (2a) promoting the adhesion of a primer layer (4a) on the support (2);

[0226] c) a step of applying layers (4a), optionally (4b), and (4c) of the coating (4);

[0227] d) optionally a drying step between 50°C and 150°C after application of said layers;

[0228] e) a cooking step of the element obtained in step c) or d) at a temperature between 250°C and 420°C;

[0229] f) a step of shaping the element obtained to give it the shape of a support (2) of convex or hollow shape defining an inner face (21) concave and an outer face (22) convex.

[0230] Advantageously, in step c), the layer(s) (4a), (4b) and (4c) is / are applied by pad printing, electrostatic powder coating, spraying, screen printing, roller application or digital printing, preferably by spraying. Advantageously, the spraying is carried out in a solvent-based or aqueous phase.

[0231] Advantageously, when layer (4c) is made up of:

[0232] - of a silicone elastomer obtained from at least one organopolysiloxane carrier of vinyl reactive functions (-CH=CH2), at least one other organopolysiloxane bearing silyl hydride (Si-H) reactive functions, preferably in the presence of a metallic catalyst; and possibly:

[0233] - of one or more thermoplastics

[0234] - of one or more charge(s), and / or

[0235] - of one or more additive(s), and / or

[0236] - of one or more coloring agents

[0237] when at least one layer (4b) is present, the process according to the invention may include a crosslinking step g) of the topcoat (4c) subsequent to or simultaneous with step d).

[0238] According to one variant, the crosslinking of the layer composition (4c) can generally be activated, for example, by heat treatment, at a temperature between 50 and 400°C, preferably between 50 and 300°C, taking into account, of course, the maximum resistance of the support to heat.

[0239] Advantageously, the crosslinking g) of the layer (4c) is carried out at a temperature of 300°C for a duration of 10 min.

[0240] Advantageously, the higher the crosslinking temperature, the shorter the crosslinking time.

[0241] According to one variant, the crosslinking step g) does not require heat treatment, in particular because the support is hot at the time of step g).

[0242] Advantageously, in step c), this topcoat (4c) is applied by electrostatic powder coating, spray spraying, screen printing, gun, squeegee, coating cylinder, brush, roller application or digital printing, preferably by spraying.

[0243] According to an advantageous arrangement of the invention, this finishing layer (4c) is applied to the coated substrate at a deposition rate of less than or equal to 5 g / m2, preferably between 0.1 and 2.5 g / m2, even more preferably between 0.2 and 2 g / m2.

[0244] Advantageously, the steps of the process according to the invention allow the metallic substrate (2) to be coated with a coating (4) formed by layers (4a), optionally (4b) and (4c). Generally, these layers are wet during their application. For the purposes of this invention, a wet layer means a layer comprising all or part of its solvents.

[0245] The shaping process is also called stamping.

[0246] When the shaping step precedes the application d) of the coating, the coating is preferably carried out by spraying.

[0247] When this shaping step is subsequent to the application d) of the coating, the coating is preferably carried out by screen printing or by roller.

[0248] ARTICLE

[0249] The invention also relates to a cooking article or an electric cooking appliance comprising a cooking element coated according to the invention or capable of being obtained according to the process of the invention.

[0250] Advantageously, the culinary article (100) according to the invention is chosen from the group consisting of saucepan, frying pan, fondue or raclette pan, stockpot, wok, sauté pan, crepe pan, grill, griddle, pot, casserole dish, cooker or bread machine bowl, cooking mold, molds and baking trays, barbecue trays and grills, preparation bowls.

[0251] According to one embodiment, the cooking article (100) has a heating face (6) intended to be brought into contact with an external heating source, the heating face (6) being opposite the cooking face (5) intended to be brought into contact with the food during cooking.

[0252] The culinary article according to the present invention may in particular be a culinary article in which one of the two opposite faces of the substrate is an interior face, possibly concave, intended to be disposed on the side of food that may be introduced into or onto said article, and in which the other face of the substrate is an exterior face, possibly convex, intended to be disposed towards a heat source.

[0253] Advantageously, the electric cooking appliance (200) is chosen from the group consisting of electric crepe maker, electric raclette appliance, electric fondue appliance, electric grill, electric plancha, electric cooker, bread machine, electric pressure cooker, waffle makers, rice cookers and jam makers.

[0254] The electric cooking appliance (200) comprises a coated cooking element (1) according to the invention and a heating source (210) configured to heat said coated cooking element (1). EXAMPLES

[0255] The aims, aspects and advantages of the present invention will be better understood from the following description of a particular embodiment of the invention presented by way of non-limiting example.

[0256] Of course, the invention is in no way limited to the embodiment described and illustrated, which has been given only by way of example. Modifications remain possible, particularly with regard to the composition of the various elements or by substitution of technical equivalents, without departing from the scope of protection of the invention.

[0257] 1) Implementation examples:

[0258] Raw materials: - PES resin • PolyEtherSulfone (PES) powder resin, micronized grade from SUMITOMO, polymer powder with a d50 between 11 and 15 pm. - Solvents: • propionamide - Reinforcement charges: • Alumina, • Silicon Carbide • Pyrogenated silica, • Colloidal silica • Colloidal alumina • Mica - Thickener: • 50% acrylic polymer solution in water • hydrogenated castor oil - Silicone resins: • Methylphenyl silicone resin, in flakes • Methyl silicone resin, in flakes - Alcohol solvent • dipropylene glycol butyl ether (DPNB), • MPG propylene glycol - Surfactant: • Fatty alcohol polyglycol ether - Anti-foaming agent • Mineral oil - Pigments: • Mica or glitter • Carbon black: - Silicone oil: • A: non-reactive • B: reactive - Other additives: • buffer agent • anionic ester in ethanol / water, wetting agent, • Aqueous dispersion of polydimethylsiloxane gum, surface tension agent

[0259] Examples of embodiments of a culinary article according to the invention:

[0260] On a flat aluminum disc (30 cm in diameter), previously degreased and sandblasted to obtain a roughness of 4 to 7 pm (Ra), a continuous layer 3a chosen from the base layer compositions (4al and 4a2) as described below is deposited by screen printing: Layers 4a#:

[0261] Layer 4al:

[0262] [Tables2] Material Nature % wet % in film Solvent DEMINERALIZED WATER 29.57 0.00 Solvent PROPIONAMIDE 22.18 0.00 Thermoplastic polymer PES 18.48 59.19 Wetting agent Fatty alcohol polyglycol ether 0.52 0.07 Acrylic thickener Acrylic polymer solution (50% in water) 5.48 1.95 Buffering agent Amino alcohol 1.05 0.00 Pigment Carbon black 4.13 4.14 Defoamer Mineral oil 1.24 0.20 Reinforcing filler Colloidal silica 4.13 4.01 Reinforcing filler Colloidal alumina 9.50 18.41 Reinforcing filler Silicon carbide 3.72 12.03 100.00 100 Layer 4a2#:

[0263] [Tables3] Material Nature % moisture content % in cured film Silicone resin Methyl or methylphenyl silicone resin 18.75 45.07 Solvent Alcohol Glycol ether 18.75 0.00 Thickener Hydrogenated castor oil 0.62 1.45 Reinforcing filler Mica 1.87 4.79 Reinforcing filler Fumed silica 1.25 3.20 Pigment Carbon black 3.75 2.97 Reinforcing filler Alumina 1.87 4.79 Wetting agent Fatty alcohol polyglycol ether 1.19 0.12 Solvent DEMINERALIZED WATER 14.56 0.00 Solvent PROPIONAMIDE 10.92 0.00 Thermoplastic polymer PES 10.92 27.66 Acrylic thickener 50% acrylic polymer solution in water 0.73 0.21 Buffering agent Amino alcohol 0.11 0.00 Spreading agent Anionic ester in ethanol / water 1.25 1.12 Solvent Alcohol Propylene glycol 5.94 0.00 Reinforcing filler Colloidal alumina 3.75 5.74 Reinforcing filler Colloidal silica 3.75 2.88 100.00 100

[0264] The thickness of this base layer 4a of the example is between 5 pm and 15 pm.

[0265] The substrate, onto which the continuous base coat 4a is applied as described above, is coated with a multilayer non-stick coating consisting of an intermediate layer 4b (5-15pm) which is dried at 80°C and a top coat 4c (5-15pm). The entire assembly is then heated to 300°C for approximately 10 minutes, meaning that the process comprises only one baking step after the deposition of the various layers. Layers 4b#:

[0266] The compositions of the intermediate layers 4b deposited by screen printing are as described below (layer 4b 1 and layer 4b2).

[0267] Layer 4b 1:

[0268] [Tables4] Material Nature % moisture % in film Solvent DEMINERALIZED WATER 33.63 0.00 Solvent PROPIONAMIDE 25.22 0.00 Thermoplastic polymer PES 21.02 79.52 Wetting agent Fatty alcohol polyglycol ether 0.59 0.09 Acrylic thickener 50% acrylic polymer solution in water 6.23 2.62 Buffering agent Amino alcohol 1.19 0.00 Pigment Carbon black 4.70 5.57 Antifoam Mineral oil 1.41 0.27 Reinforcing filler Colloidal silica 4.14 4.75 Reinforcing filler Mica 1.40 5.35 Pigment Glitter 0.48 1.83 100.00 100

[0269] Layer 4b2:

[0270] [Tables5] Material Nature % moisture content % in cured film Silicone resin Methyl or methylphenyl silicone resin 21.62 51.39 Solvent Alcohol Glycol ether 21.62 0.00 Thickener Hydrogenated castor oil 0.72 1.66 Reinforcing filler Mica 1.08 2.73 Reinforcing filler Fumed silica 1.44 3.65 Pigment Carbon black 4.32 3.39 Wetting agent Fatty alcohol polyglycol ether 1.08 0.11 Solvent DEMINERALIZED WATER 11.19 0.00 Solvent PROPIONAMIDE 8.40 0.00 Thermoplastic polymer PES 8.40 21.02 Acrylic thickener 50% acrylic polymer solution in water 0.56 0.16 Buffering agent Amino alcohol 0.09 0.00 Spreading agent Anionic ester in ethanol / water 1.44 1.28 Surface tensioning agent Aqueous dispersion of polydimethylsiloxane gum 0.72 0.97 Solvent Alcohol Propylene glycol 6.49 0.00 Reinforcing filler Colloidal alumina 7.21 10.92 Reinforcing filler Colloidal silica 3.60 2.73 100.00 100

[0271] The compositions of the 4c ​​finishing layers deposited by screen printing are as described below (layers 4c 1 to 4c4): Top coat (4c)

[0272] Layer 4cl:

[0273] [Tableauxô] Material Nature %wet % in baked film Solvent DEMINERALIZED WATER 39.4 0.00 Solvent PROPIONAMIDE 29.55 0.00 Thermoplastic polymer PES 24.62 91.15 Wetting agent Fatty alcohol polyglycol ether 0.69 0.10 Acrylic thickener 50% acrylic polymer solution in water 3.44 1.42 Buffering agent Amino alcohol 0.3 0.00 Silicone oil A 2.00 7.33 100 100

[0274] Layer 4c2:

[0275] [Tables7] Material Nature % moisture content % in cured film Silicone resin Methyl or methylphenyl silicone resin 30.00 70.62 Solvent Alcohol Glycol ether 39.60 0.00 Reinforcing filler Fumed silica 1.00 2.50 Thickener Hydrogenated castor oil 1.70 3.87 Wetting agent Fatty alcohol polyglycol ether 1.65 0.17 Solvent DEMINERALIZED WATER 8.54 0.00 Solvent PROPIONAMIDE 6.41 0.00 Thermoplastic polymer PES 6.41 15.89 Acrylic thickener 50% acrylic polymer solution in water 0.43 0.12 Buffering agent Amino alcohol 0.06 0.00 Spreading agent Anionic ester in ethanol / water 1.50 1.31 Surface tensioning agent: Aqueous dispersion of polydimethylsiloxane gum 1.00 1.33 Silicone oil B 1.00 2.45 Silicone oil A 0.50 1.23 Pigment: Glitter 0.20 0.50 100.00 100

[0276] Layer 4c3:

[0277] [Tables8] Material Nature % moisture content % in cured film Silicone resin Methyl or methylphenyl silicone resin 7.1 23.44 Solvent Alcohol Glycol ether 7.1 0.00 Thickener Hydrogenated castor oil 0.1 0.32 Reinforcing filler Fumed silica 0.2 0.70 Wetting agent Fatty alcohol polyglycol ether 0.4 0.06 Solvent Alcohol Propylene glycol 12.82 0.00 Spreading agent Anionic ester in ethanol / water 0.35 0.43 Defoamer Mineral oil 0.7 0.12 Solvent Demineralized water 27.3 0.00 Solvent Propionamide 20.48 0.00 Thermoplastic polymer PES 20.48 71.21 Wetting agent Fatty alcohol polyglycol ether 0.48 0.07 Acrylic thickener 50% acrylic polymer solution in water 1.39 0.54 Buffering agent Amino alcohol 0.2 0.00 Silicone oil A 0.7 2.41 Pigment Glitter 0.2 0.70 100 100

[0278] Layer 4c4:

[0279] [Tables9] Material Nature % moisture content % in cured film Silicone resin Methyl or methyl-phenethyl silicone resin 30.00 84.33 Solvent Alcohol Glycol ether 41.70 0.00 Thickener Hydrogenated castor oil 1.60 4.35 Reinforcing filler Fumed silica 1.00 2.99 Wetting agent Fatty alcohol polyglycol ether 1.50 0.18 Solvent Alcohol Propylene glycol 20.00 0.00 Spreading agent Anionic ester in ethanol / water 1.50 1.57 Surface tensioning agent Aqueous dispersion of polydimethylsiloxane gum 1.00 1.58 Silicone oil B 1.00 2.93 Silicone oil A 0.50 1.47 Pigment Glitter 0.20 0.60 100.00 100

[0280] Examples of construction / architecture of heating elements according to the invention:

[0281] [TableauxlO] 1 2 3 Base coat al a2 al Intermediate coat bl b2 bl Top coat cl c2 c3

Claims

Demands

1. Coated cooking element (1) for a cooking article or electrical cooking appliance, comprising a metallic substrate (2) coated on at least one face (2a) by a coating (3) intended to form a cooking face free of fluorocarbon resin and coated on at least the other face (2b) by a coating (4) comprising at least the following layers and in this order from the metallic substrate (2): - (4a) primer layer comprising polyethersulfone (PES), - (4b) optionally, one or more intermediate layer(s) comprising polyethersulfone (PES) or a mixture of polyethersulfone (PES) and one or more silicone resins, - (4c) top layer comprising polyethersulfone (PES) or one or more silicone resins or a mixture of polyethersulfone (PES) and one or more silicone resins.

2. Coated cooking element (1) according to claim 1, characterized in that the PES content is increasing from the primer layer (4a) to the finishing layer (4c).

3. Coated cooking element (1) according to claim 2, characterized in that the PES content of the primer layer (4a) represents from 50% to less than 75% by weight of the primer layer (4a).

4. Coated cooking element (1) according to any one of the preceding claims, characterized in that the PES content of the intermediate layer(s) (4b) represents from 75% to less than 85% by weight of said layer(s) when it is / are present.

5. Coated cooking element (1) according to any one of the preceding claims, characterized in that the PES content of the finishing layer (4c) represents from 85% to 98% by weight of the finishing layer (4c).

6. Coated cooking element (1) according to any one of the preceding claims, characterized in that the thickness of each of the coating layers (4a), (4b) and (4c) is from 5 pm to 15 pm.

7. Coated cooking element (1) according to claim 1, characterized in that the finishing layer (4c) is made up of: - of a silicone elastomer obtained from at least one organopolysiloxane bearing vinyl reactive functions (-CH=CH 2), at least one other organopolysiloxane bearing silyl hydride reactive functions (Si-H), preferably in the presence of a metallic catalyst; and possibly: - of one or more thermoplastics, and / or - of one or more additive(s), and / or - of one or more coloring agents when at least one layer (4b) is present.

8. A method for manufacturing a cooking article or electric cooking appliance comprising a cooking element coated (1) with a coating (4) according to any one of the preceding claims, characterized by the following steps: a) a step of supplying a metallic substrate (2) in the form of a substantially flat metallic substrate comprising two opposite faces; b) optionally, a step of treating at least one face (2a) of the metallic substrate (2), to obtain a treated face (2a) promoting the adhesion of a primer layer (4a) to the support (2); c) a step of applying the layers (4a), optionally (4b), and (4c) of the coating (4); d) optionally a drying step between 50°C and 150°C after application of said layers; e) a step of baking the element obtained in step c) or d) at a temperature between 250°C and 420°C.f) a shaping step of the element obtained to give it the shape of a support (2) of convex or hollow shape defining an inner face (21) concave and an outer face (22) convex.

9. Cooking article or electric cooking appliance comprising a coated cooking element (1) according to any one of claims 1 to 7 or capable of being obtained according to claim 8 characterized in that the layer (4c) is intended to be brought into contact with a heating source.

10. A cooking article (100) according to claim 9, selected from the group consisting of a saucepan, frying pan, fondue or raclette pan, stockpot, wok, sauté pan, crepe pan, grill, griddle, casserole dish, cooking pot or bread machine bowl, mold culinary, baking molds and trays, barbecue trays and grills, preparation bowls.

11. Electric cooking appliance (200) according to claim 9, selected from the group consisting of electric crepe maker, electric raclette appliance, electric fondue appliance, electric grill, electric griddle, electric cooker, bread maker, electric pressure cooker, waffle makers, rice cookers and jam makers.

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