EP3908639A1 - Anti-adhesive coating - Google Patents

Anti-adhesive coating

Info

Publication number
EP3908639A1
EP3908639A1 EP19824333.9A EP19824333A EP3908639A1 EP 3908639 A1 EP3908639 A1 EP 3908639A1 EP 19824333 A EP19824333 A EP 19824333A EP 3908639 A1 EP3908639 A1 EP 3908639A1
Authority
EP
European Patent Office
Prior art keywords
fillers
coating according
finishing layer
coating
finishing
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.)
Pending
Application number
EP19824333.9A
Other languages
German (de)
French (fr)
Inventor
Romain BESNARD
Aurélien DUBANCHET
Laurent Caillier
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.)
SEB SA
Original Assignee
SEB SA
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 SEB SA filed Critical SEB SA
Publication of EP3908639A1 publication Critical patent/EP3908639A1/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
    • A47J36/00—Parts, details or accessories of cooking-vessels
    • A47J36/02—Selection of specific materials, e.g. heavy bottoms with copper inlay or with insulating inlay
    • A47J36/025—Vessels with non-stick features, e.g. coatings
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • 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
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/04—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • B05D2202/00—Metallic substrate
    • 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
    • B05D2601/00—Inorganic fillers
    • B05D2601/20—Inorganic fillers used for non-pigmentation effect
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium

Definitions

  • the present invention relates to the field of non-stick coatings intended to be applied to articles, and more particularly to household articles, such as cookware or household appliances.
  • thermostable resin-based coatings including polytetrafluoroethylene (PTFE).
  • PTFE polytetrafluoroethylene
  • This durability is generally evaluated by the appearance of scratches on the metal and the wear of the coating which results in a loss of non-stickiness.
  • PTFE polytetrafluoroethylene
  • These attributes are generally covered by a transparent top coat of PTFE which guarantees an optimum level of non-sticking.
  • this does not make it possible to durably protect the above-mentioned attributes from the mechanical stresses inherent in the use of the article (abrasion, scratch ).
  • WO 2007/070601 describes coatings having a finishing layer comprising diamond particles. The use of such particles poses a problem in the cost of manufacturing the product comprising the coating.
  • the Applicant has developed a non-stick coating comprising a finishing layer which overcomes the aforementioned drawbacks.
  • this non-stick coating has optical properties compatible with the presence of visual attributes in the coating and makes it possible to increase the durability of the coating in the face of mechanical stresses, without degrading the non-stick coating.
  • the present invention therefore relates to a non-stick coating comprising a transparent finishing layer, said finishing layer comprising at least one thermostable resin and fillers whose d50 is greater than the average thickness of said finishing layer.
  • the present invention also relates to an article comprising a support provided with the non-stick coating according to the invention.
  • finishing layer (sometimes referred to as “finish") is meant in the sense of the present invention the final coating layer, that is to say the coating layer intended to be in contact with the external environment.
  • transparent layer is meant, within the meaning of the present invention, a layer which allows light to pass through it over the entire visible range, that is to say which must have a direct transmittance greater than 90% and a total Haze value less than 40%.
  • the transparent topcoat of the coating according to the invention must have a direct transmittance greater than 90% and a totalized Haze value less than 40%.
  • the finishing layer of the coating according to the invention is easily distinguishable from the layers on which it is deposited by sectional observations using a scanning electron microscope (SEM) or an optical microscope. By analyzing microscopic images, the thickness of the top coat can be measured. The thickness of the finishing layer is measured at 20 random points on the section of the coating. The average thickness of the top coat is obtained by averaging these 20 measurements.
  • SEM scanning electron microscope
  • the top layer has an average thickness of 2 to 40 ⁇ m, preferably from 10 to 30 ⁇ m.
  • the d50 corresponds to the 50th percentile of the volume distribution of particle size, that is to say that 50% of the volume represents particles which have a size less than or equal to d50 and 50% of the particles which are larger than d50.
  • the dv50 is defined similarly.
  • the d50 is measured by laser particle size.
  • the fillers have a d50 at least 1.4 times greater, preferably at least 1.5 times greater, than the average thickness of said top coat.
  • the fillers have a d50 which is at most, 3 times greater, preferably 2 times greater, than the average thickness of said top coat.
  • the load d50 is less than 1.4 times the average thickness of the topcoat, the optimal abrasion-resistant properties are no longer guaranteed. Conversely, if the d50 of the fillers is greater than 3 times the thickness of the top coat, this leads to a loss of non-stick coating.
  • the fillers have a d50 greater than 2 pm.
  • the fillers have a d50 greater than 20 ⁇ m, and preferably greater than 30 ⁇ m.
  • the fillers have a d50 of less than 120 ⁇ m.
  • the fillers have a d50 of less than 60 ⁇ m, and preferably less than 50 ⁇ m.
  • the fillers are mineral fillers having a Mohs hardness greater than or equal to 7.
  • fillers which can be used in the context of the present invention, mention may in particular be made of metal oxides, metal carbides, metal oxy-nitrides, metal nitrides, and mixtures thereof.
  • the fillers are chosen from alumina, silicon carbide, zirconia, tungsten carbide, boron nitride, quartz, and their mixtures.
  • the fillers used are metal oxides, preferably chosen from alumina, zirconia, quartz and their mixtures.
  • the metal oxides are alumina.
  • the finishing layer comprises from 0.5 to 20% of fillers, more preferably from 1 to 10%, percentages expressed in dry mass relative to the total dry mass of the finishing layer .
  • the size, and therefore the d50, as well as the concentration of the charges in the finishing layer can be evaluated by carrying out an observation with a crossed optical microscope with a scanning electron microscope (SEM) provided with an EDS on the surface of the coating according to l 'invention.
  • SEM scanning electron microscope
  • a 1 cm 2 mapping provides a representative observation of the sample.
  • the chemical composition of each charge is then determined by energy dispersive analyzes using a scanning electron microscope (SEM) equipped with an EDS.
  • the particle size distribution is measured by computer and digital image processing. This makes it possible to determine the d50 as well as the average volume of the charges and therefore to determine the concentration.
  • the volume concentration of the fillers can be calculated from the ratio of the volume of the fillers to the sum of the volume of the fillers and the top coat.
  • the mass concentration is then calculated, taking account respectively of the density of the fillers and of the finishing layer.
  • the top coat according to the invention comprises at least one thermostable resin.
  • a thermostable resin is a resin resistant to at least 200 ° C.
  • thermostable resin of the top layer is a fluorocarbon resin, preferably chosen from polytetrafluoroethylene (PTFE), copolymers of tetrafluoroethylene and perfluoromethylvinyl ether (such as MFA), copolymers of tetrafluoroethylene and perfluoropropylvinylether (such as PFA), copolymers of tetrafluoroethylene and hexafluoropropylene (such as FEP) and their mixtures.
  • PTFE polytetrafluoroethylene
  • MFA perfluoromethylvinyl ether
  • PFA perfluoropropylvinylether
  • FEP hexafluoropropylene
  • the non-stick coating according to the invention may also comprise at least one layer of primer (sometimes referred to as “bonding primer” or “primer”).
  • This primer layer is intended to be in contact with the surface of the support of the article on which the coating will be deposited.
  • this primer layer allows the coating to hang on the support.
  • the non-stick coating according to the invention may also further comprise at least one intermediate layer (sometimes referred to as "midcoat”) between the primer layer and the top coat.
  • at least one intermediate layer sometimes referred to as "midcoat”
  • the non-stick coating according to the invention may further comprise attributes, such as a decoration or an article-specific functionality such as an indicator of optimal cooking temperature. These attributes are applied between the primer and the topcoat if the coating does not include an intermediate layer or between the intermediate layer and the topcoat otherwise.
  • the present invention also relates to an article comprising a support provided with the non-stick coating according to the invention.
  • the article according to the invention is a household article, in particular a culinary article.
  • domestic article is meant within the meaning of the present invention an object intended to ensure the domestic needs of everyday life, in particular an article intended to receive a heat treatment or intended to produce heat.
  • it can be a culinary item or an appliance item.
  • an object which will be heated by an external heating system in particular a culinary article such as frying pans, pots, sauté pans, woks, crepe makers, pots, pots, casseroles, braising pans, casseroles, barbecue grills, baking molds, fondue pots and which is able to transmit the heat energy provided by this external heating system to a material or food contact of said object.
  • an external heating system in particular a culinary article such as frying pans, pots, sauté pans, woks, crepe makers, pots, pots, casseroles, braising pans, casseroles, barbecue grills, baking molds, fondue pots and which is able to transmit the heat energy provided by this external heating system to a material or food contact of said object.
  • the present invention therefore also relates to a culinary article comprising a support provided with the non-stick coating according to the invention.
  • the culinary article according to the invention comprises a support which has an internal face intended to receive food and an external face intended to be disposed towards a heat source, and a non-stick coating according to the invention arranged on at least one of the two faces of the support.
  • a heating object having its own heating system in particular an appliance, such as irons, hair straighteners, steam generators or appliances appliances intended for cooking like a saucer.
  • part of the article support is coated with the non-stick coating according to the invention, but it can be envisaged that the entire article support is coated.
  • the support can be made of metallic material, glass, ceramic, terracotta or plastic.
  • the support can be metallic and can be made of aluminum or aluminum alloy, anodized or not, optionally polished, brushed, sandblasted or microblasted, or steel possibly polished, brushed, sandblasted or microblasted, or stainless steel possibly polished , brushed, sandblasted or microblasted, or made of cast iron, aluminum or iron, or copper, possibly hammered or polished.
  • the support can be metallic and can comprise an alternation of layers of metal and / or metallic alloy, or is a cap of foundry aluminum, aluminum or aluminum alloys lined with an external bottom. Stainless steel.
  • the average thickness of the finishing layers was evaluated by sectional observations using a scanning electron microscope (SEM). The thickness of the finishing layers was measured at 20 random points on the cover sections. The average thickness of the topcoats was obtained by averaging these 20 measurements.
  • SEM scanning electron microscope
  • Example 1 Coating according to the invention comprising a top coat containing alumina fillers
  • a finishing formulation was prepared from a dispersion of PTFE particles approximately 200 nm in diameter. 2.5% by mass of angular charges of alumina having a d50 of 44 ⁇ m in powder form was added to the dispersion. The dry extract of the dispersion was fixed at 50% by mass. In order to keep this parameter fixed, the amount of water has been adjusted.
  • This finishing formulation was sprayed on a shaped article (a frying pan) coated beforehand with two other layers all mainly composed of PTFE: a black primer, an intermediate layer as well as decorative attributes and functional (decor and optimal cooking temperature indicator).
  • the quantity of finish formulation deposited was adjusted so as to obtain a measured average thickness of 20 ⁇ 1 ⁇ m of the finish layer after baking the article for 11 min at 430 ° C.
  • Example 2 Coating According to the Invention Comprising a Top Coat Containing Alumina Fillers
  • a first finishing formulation was prepared from a dispersion of PTFE particles approximately 200 nm in diameter. 2.5% by mass of charges Angular alumina having a d50 of 44 ⁇ m in powder form was added to the dispersion. The dry extract of the dispersion was fixed at 50% by mass. In order to keep this parameter fixed, the amount of water has been adjusted.
  • This first finishing formulation was sprayed onto a shaped article (a frying pan) coated beforehand with two other layers, all mainly composed of PTFE: a black primer, an intermediate layer as well as decorative attributes. and functional (decor and optimal cooking temperature indicator).
  • a second clear, uncharged topcoat formulation was prepared from a dispersion of PTFE particles approximately 200 nm in diameter.
  • the dry extract of the dispersion was fixed at 50% by mass. In order to keep this parameter fixed, the amount of water has been adjusted.
  • This second finishing formulation was then deposited on the first finishing formulation, by spraying.
  • the quantity of formulation deposited was adjusted so as to obtain a total average thickness measured of 25 ⁇ 1 ⁇ m after baking of the article for 11 min at 430 ° C. and so that the first formulation represents 40% of the finishing layer and that the second formulation represents 60% of the top coat.
  • Counterexample 1 Coating comprising an uncharged topcoat
  • An uncharged topcoat was prepared from a dispersion of PTFE particles about 200 nm in diameter. The dry extract of the dispersion was fixed at 50% by mass. In order to keep this parameter fixed, the amount of water has been adjusted.
  • This finishing formulation was sprayed onto a shaped article (a frying pan) coated beforehand with two other layers, all mainly composed of PTFE: a black primer, an intermediate layer as well as decorative attributes and functional (decor and optimal cooking temperature indicator).
  • the quantity of finish formulation deposited was adjusted so as to obtain a measured average thickness of 10 ⁇ 1 ⁇ m of the finishing layer after baking the article for 11 min at 430 ° C.
  • a finishing formulation was prepared from a dispersion of PTFE particles approximately 200 nm in diameter. 1% by mass of colloidal alumina fillers having a d50 of 200 nm were added to the dispersion. The dry extract of the dispersion was fixed at 50% by mass. In order to keep this parameter fixed, the amount of water has been adjusted.
  • This finishing formulation was sprayed on a shaped article (a frying pan) coated beforehand with two other layers all mainly composed of PTFE: a black primer, an intermediate layer as well as decorative attributes and functional (decor and optimal cooking temperature indicator).
  • the quantity of finish formulation deposited was adjusted so as to obtain a measured average thickness of 20 ⁇ 1 ⁇ m of the finish layer after baking the article for 11 min at 430 ° C.
  • a finishing formulation was prepared from a dispersion of PTFE particles approximately 200 nm in diameter. 2.5% by mass of angular charges of alumina having a d50 of 1 ⁇ m in powder form was added to the dispersion. The dry extract of the dispersion was fixed at 50% by mass. In order to keep this parameter fixed, the amount of water has been adjusted.
  • This finishing formulation was sprayed onto a shaped article (a frying pan) coated beforehand with two other layers, all mainly composed of PTFE: a black primer, an intermediate layer as well as decorative attributes and functional (decor and optimal cooking temperature indicator).
  • the quantity of finish formulation deposited was adjusted so as to obtain a measured average thickness of 20 ⁇ 1 ⁇ m of the finishing layer after baking the article for 11 min at 430 ° C.
  • Counter-Example 3a Coating comprising a top coat containing alumina fillers whose d50 is 1.3 times greater than the thickness of the top layer
  • a finishing formulation was prepared from a dispersion of PTFE particles approximately 200 nm in diameter. 2.5% by mass of angular charges of alumina having a d50 of 26 ⁇ m in powder form was added to the dispersion. The dry extract of the dispersion was fixed at 50% by mass. In order to keep this parameter fixed, the amount of water has been adjusted.
  • This finishing formulation was sprayed on a shaped article (a frying pan) coated beforehand with two other layers all mainly composed of PTFE: a black primer, an intermediate layer as well as decorative attributes and functional (decor and optimal cooking temperature indicator).
  • the quantity of finish formulation deposited was adjusted so as to obtain a measured average thickness of 20 ⁇ 1 ⁇ m of the finish layer after baking the article for 11 min at 430 ° C.
  • the alumina load d50 is therefore 1.3 times greater than the thickness of the top coat.
  • a finishing formulation was prepared from a dispersion of PTFE particles approximately 200 nm in diameter. 2.5% by mass of angular charges of alumina having a d50 of 44 ⁇ m in powder form were added to the dispersion. The dry extract of the dispersion was fixed at 50% by mass. In order to keep this parameter fixed, the amount of water has been adjusted.
  • This finishing formulation was sprayed on a shaped article (a frying pan) coated beforehand with two other layers all mainly composed of PTFE: a black primer, an intermediate layer as well as decorative attributes and functional (decor and optimal cooking temperature indicator).
  • the quantity of finish formulation deposited was adjusted so as to obtain a measured average thickness of 40 ⁇ 1 ⁇ m of the finish layer after baking the article for 11 min at 430 ° C.
  • the alumina load d50 is therefore 1.1 times greater than the thickness of the top coat.
  • a finishing formulation was prepared from a dispersion of PTFE particles approximately 200 nm in diameter. 2.5% by mass of angular charges of alumina having a d50 of 64 ⁇ m in powder form was added to the dispersion. The dry extract of the dispersion was fixed at 50% by mass. In order to keep this parameter fixed, the amount of water has been adjusted.
  • This finishing formulation was sprayed onto a shaped article (a frying pan) coated beforehand with two other layers, all mainly composed of PTFE: a black primer, an intermediate layer as well as decorative attributes and functional (decor and optimal cooking temperature indicator).
  • the quantity of finish formulation deposited was adjusted so as to obtain a measured average thickness of 20 ⁇ 1 ⁇ m of the finish layer after baking the article for 11 min at 430 ° C.
  • the d50 of the alumina filler is therefore 3.2 times greater than the thickness of the finishing layer.
  • This test evaluates the resistance of the coating to the action of an abrasive pad applied to its surface and the drop in non-sticking of this coating by a milk carbonization test after it has been subjected to the abrasion cycle. . It is based on a normative test: NF D 21 -51 1 with specific features.
  • the device used is an abrasimeter with a horizontal movement.
  • a fixed arm supports a rectangular pad of dimensions 70 ⁇ 5 mm x 30 ⁇ 5 mm, on which is placed an abrasive pad of the same dimension, and includes a tare allowing the application of a load of 21 N (mass of the arm of lever included).
  • the abrasive moves at the speed of 33 back and forth per minute.
  • the abraded surface is 70 mm x 130 mm, i.e. a stroke of 100 mm.
  • 1000 abrasion cycles i.e. 1000 round trips of the abrasive
  • the evolution of the anti-adhesion is evaluated after carbonization of a film of milk.
  • the test is stopped at the appearance of a scratch or a loss of non-stick (milk hooked irreversibly even after cleaning).
  • v is proportional to K, to the modulus of the normal force » M ' ⁇ (21 N) and to the distance traveled d (ie 200 m).
  • finishing formulations of the above examples and counterexamples were each applied directly to an enameled and smooth plate.
  • the quantity of finish formulation deposited was adjusted so as to obtain the same average thicknesses of finish layer as those of the examples and counterexamples, after baking the plate for 11 min at 430 ° C.
  • the films thus obtained were removed from the plates and analyzed.
  • a coating must contain a top coat with a higher direct transmittance 90% and whose total Haze value is less than 40%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Food Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Cookers (AREA)

Abstract

The present invention relates to an anti-adhesive coating comprising a transparent finish layer, said finish layer comprising at least one thermostable resin and fillers, the d50 of which is greater than the average thickness of said finish layer.

Description

REVETEMENT ANTIADHESIF NON-STICKING COATING
DOMAINE TECHNIQUE TECHNICAL AREA
La présente invention concerne le domaine des revêtements antiadhésifs destinés à être appliqués sur des articles, et plus particulièrement sur des articles domestiques, tels que des articles culinaires ou électroménagers. The present invention relates to the field of non-stick coatings intended to be applied to articles, and more particularly to household articles, such as cookware or household appliances.
TECHNIQUE ANTERIEURE PRIOR ART
Dans l’industrie des articles culinaires, la durabilité mécanique des revêtements à base de résine thermostable, notamment à base de polytétrafluoroéthylène (PTFE), est l’une des plus importantes préoccupations. Cette durabilité est généralement évaluée par l’apparition de rayures au métal et de l’usure du revêtement qui se traduit par une perte d’antiadhésivité. Par ailleurs, il est courant de trouver dans le fond des articles un décor et/ou une fonctionnalité spécifique à l’article comme un indicateur de température optimale de cuisson. Ces attributs sont généralement recouverts par une couche de finition transparente de PTFE qui garantit un niveau d’antiadhésivité optimum. Cependant, cela ne permet pas de protéger durablement les attributs précités face aux sollicitations mécaniques inhérentes à l’utilisation de l’article (abrasion, rayure...). One of the most important concerns in the cookware industry is the mechanical durability of thermostable resin-based coatings, including polytetrafluoroethylene (PTFE). This durability is generally evaluated by the appearance of scratches on the metal and the wear of the coating which results in a loss of non-stickiness. In addition, it is common to find in the bottom of the articles a decor and / or a functionality specific to the article as an indicator of optimal temperature of cooking. These attributes are generally covered by a transparent top coat of PTFE which guarantees an optimum level of non-sticking. However, this does not make it possible to durably protect the above-mentioned attributes from the mechanical stresses inherent in the use of the article (abrasion, scratch ...).
L’utilisation de revêtement composite conçu par l’incorporation de charges renforçantes est une technique très connue de l’homme de l’art (US8642171 , US8728993, US5665450) pour améliorer la résistance à l’abrasion et retarder l’apparition de la rayure. Les susmentionnées performances dépendent de la nature, de la taille et de la concentration de charges incorporées dans le revêtement. McEIwain et coll. (« Effect of Particle Size on the Wear Résistance of Alumina-Filled PTFE Micro- and Nanocomposites » - Tribol. Trans. 2008,51 (3), 247-253) ont notamment exploré l’effet de la taille des charges (ou particules) sur les performances d’abrasion. Il en ressort qu’il est possible de gagner jusqu’à 2 ordres de grandeur sur la résistance à l’usure pour des charges de taille micrométrique et presque 4 ordres pour des charges de taille nanométrique. The use of composite coating designed by the incorporation of reinforcing fillers is a technique very well known to those skilled in the art (US8642171, US8728993, US5665450) to improve abrasion resistance and delay the appearance of the scratch. . The aforementioned performance depends on the nature, size and concentration of fillers incorporated in the coating. McEIwain et al. (“Effect of Particle Size on the Wear Résistance of Alumina-Filled PTFE Micro- and Nanocomposites” - Tribol. Trans. 2008,51 (3), 247-253) notably explored the effect of the size of the charges (or particles ) on abrasion performance. It turns out that it is possible to gain up to 2 orders of magnitude on the resistance to wear for loads of micrometric size and almost 4 orders for loads of nanometric size.
L’inconvénient de l’incorporation de charges renforçantes dans les revêtements PTFE est qu’elle peut, d’une part, entraîner une diminution des propriétés antiadhésives, et d’autre part, entraîner la baisse de la transparence. En effet, cela peut conduire à augmenter la diffusion de la lumière dans la couche chargée, et altérer l’esthétique du revêtement dépendamment de la nature, de la taille et de la quantité de charges incorporée dans le revêtement. The disadvantage of incorporating reinforcing fillers into PTFE coatings is that it can, on the one hand, lead to a reduction in properties. non-stick, and on the other hand, result in lower transparency. Indeed, this can lead to increasing the scattering of light in the charged layer, and altering the aesthetics of the coating depending on the nature, size and amount of fillers incorporated in the coating.
Le document WO 2007/070601 décrit des revêtements ayant une couche de finition comprenant des particules de diamant. L’utilisation de telles particules pose un problème de coût de fabrication du produit comprenant le revêtement. WO 2007/070601 describes coatings having a finishing layer comprising diamond particles. The use of such particles poses a problem in the cost of manufacturing the product comprising the coating.
Dans le contexte des articles culinaires, l’utilisation de charges renforçantes dans les couches supérieures du revêtement est très limitée. En effet, ces modifications de propriétés optiques peuvent ne pas être compatibles avec la mise en place de décors et de fonctionnalités sous la ou les couches de finition protectrices dans le fond des articles culinaires permettant d’en améliorer l’attractivité. Pour pallier ces problématiques optiques, l’utilisation de charges inorganiques de tailles inférieures à 100 nm est connue. Cependant, l’incorporation de ce type de charges entraîne une perte significative des propriétés anti-adhésives du revêtement. In the context of cookware, the use of reinforcing fillers in the upper layers of the coating is very limited. Indeed, these changes in optical properties may not be compatible with the setting up of decorations and functionalities under the protective finishing layer (s) in the bottom of the cookware making it possible to improve its attractiveness. To overcome these optical problems, the use of inorganic fillers of sizes less than 100 nm is known. However, the incorporation of this type of filler results in a significant loss of the non-stick properties of the coating.
EXPOSE DE L'INVENTION STATEMENT OF THE INVENTION
Il est donc devenu nécessaire de proposer des revêtements présentant une durabilité améliorée face à des contraintes mécaniques sans altération des caractéristiques antiadhérentes et des propriétés visuelles de ces revêtements. La demanderesse a mis au point un revêtement antiadhésif comprenant une couche de finition permettant d'obvier les inconvénients précités. It has therefore become necessary to provide coatings having improved durability in the face of mechanical stresses without altering the non-stick characteristics and the visual properties of these coatings. The Applicant has developed a non-stick coating comprising a finishing layer which overcomes the aforementioned drawbacks.
Les avantages de ce revêtement antiadhésif sont que ladite couche de finition présente des propriétés optiques compatibles avec la présence d’attributs visuels dans le revêtement et permet d’augmenter la durabilité du revêtement face aux contraintes mécaniques, sans dégradation de l’antiadhérence du revêtement. The advantages of this non-stick coating are that said top layer has optical properties compatible with the presence of visual attributes in the coating and makes it possible to increase the durability of the coating in the face of mechanical stresses, without degrading the non-stick coating.
La présente invention a donc pour objet un revêtement antiadhésif comprenant une couche de finition transparente, ladite couche de finition comprenant au moins une résine thermostable et des charges dont le d50 est supérieur à l’épaisseur moyenne de ladite couche de finition. The present invention therefore relates to a non-stick coating comprising a transparent finishing layer, said finishing layer comprising at least one thermostable resin and fillers whose d50 is greater than the average thickness of said finishing layer.
La présente invention a également pour objet un article comprenant un support muni du revêtement antiadhésif selon l’invention. Par couche de finition (parfois mentionnée comme « finish »), on entend au sens de la présente invention la couche finale du revêtement, c'est-à-dire la couche du revêtement destinée à être en contact avec l’environnement extérieur. The present invention also relates to an article comprising a support provided with the non-stick coating according to the invention. By finishing layer (sometimes referred to as "finish") is meant in the sense of the present invention the final coating layer, that is to say the coating layer intended to be in contact with the external environment.
Par couche transparente, on entend, au sens de la présente invention, une couche qui se laisse traverser par la lumière sur l'ensemble du domaine visible, c’est-à-dire qui doit présenter une transmittance directe supérieure à 90% et une valeur de Haze totalisée inférieure à 40%. By transparent layer is meant, within the meaning of the present invention, a layer which allows light to pass through it over the entire visible range, that is to say which must have a direct transmittance greater than 90% and a total Haze value less than 40%.
La couche de finition transparente du revêtement selon l’invention doit présenter une transmittance directe supérieure à 90% et une valeur de Haze totalisée inférieure à 40%. The transparent topcoat of the coating according to the invention must have a direct transmittance greater than 90% and a totalized Haze value less than 40%.
La couche de finition du revêtement selon l’invention est aisément différentiable des couches sur lesquelles elle est déposée par observations en coupe au microscope électronique à balayage (MEB) ou au microscope optique. Par l’analyse des images microscopiques, l’épaisseur de la couche de finition est mesurable. La mesure de l’épaisseur de la couche de finition est réalisée en 20 points aléatoires sur la coupe du revêtement. L'épaisseur moyenne de la couche de finition est obtenue en faisant la moyenne de ces 20 mesures. The finishing layer of the coating according to the invention is easily distinguishable from the layers on which it is deposited by sectional observations using a scanning electron microscope (SEM) or an optical microscope. By analyzing microscopic images, the thickness of the top coat can be measured. The thickness of the finishing layer is measured at 20 random points on the section of the coating. The average thickness of the top coat is obtained by averaging these 20 measurements.
Avantageusement, la couche de finition présente une épaisseur moyenne de 2 à 40 pm, de préférence de 10 à 30 pm. Advantageously, the top layer has an average thickness of 2 to 40 μm, preferably from 10 to 30 μm.
Le d50, également noté dv50, correspond au 50ème centile de la distribution en volume de taille des particules, c'est-à-dire que 50% du volume représente des particules qui ont une taille inférieure ou égale au d50 et 50% des particules qui ont une taille supérieure au d50. Le dv50 est défini de manière similaire. Le d50 est mesuré par granulométrie laser. The d50, also denoted dv50, corresponds to the 50th percentile of the volume distribution of particle size, that is to say that 50% of the volume represents particles which have a size less than or equal to d50 and 50% of the particles which are larger than d50. The dv50 is defined similarly. The d50 is measured by laser particle size.
De manière avantageuse, les charges ont un d50 au moins 1 ,4 fois supérieur, de préférence au moins 1 ,5 fois supérieur, à l’épaisseur moyenne de ladite couche de finition. Préférentiellement, les charges ont un d50 qui est au maximum, 3 fois supérieur, de préférence 2 fois supérieur, à l’épaisseur moyenne de ladite couche de finition. Advantageously, the fillers have a d50 at least 1.4 times greater, preferably at least 1.5 times greater, than the average thickness of said top coat. Preferably, the fillers have a d50 which is at most, 3 times greater, preferably 2 times greater, than the average thickness of said top coat.
Si le d50 des charges est inférieur à 1 ,4 fois l’épaisseur moyenne de la couche de finition, les propriétés d’anti-abrasion optimales ne sont plus assurées. Inversement, si le d50 des charges est supérieur à 3 fois l’épaisseur de la couche de finition, cela conduit à une perte d’antiadhésivité du revêtement. If the load d50 is less than 1.4 times the average thickness of the topcoat, the optimal abrasion-resistant properties are no longer guaranteed. Conversely, if the d50 of the fillers is greater than 3 times the thickness of the top coat, this leads to a loss of non-stick coating.
Préférentiellement, les charges ont un d50 supérieur à 2 pm. Avantageusement, les charges ont un d50 supérieur à 20 pm, et de préférence supérieur à 30 pm. Preferably, the fillers have a d50 greater than 2 pm. Advantageously, the fillers have a d50 greater than 20 μm, and preferably greater than 30 μm.
Préférentiellement, les charges ont un d50 inférieur à 120 pm. Avantageusement, les charges ont un d50 inférieur à 60 pm, et de préférence inférieur à 50 pm. Preferably, the fillers have a d50 of less than 120 μm. Advantageously, the fillers have a d50 of less than 60 µm, and preferably less than 50 µm.
Avantageusement, les charges sont des charges minérales présentant une dureté de Mohs supérieure ou égale à 7. Advantageously, the fillers are mineral fillers having a Mohs hardness greater than or equal to 7.
A titre de charges utilisables dans le cadre de la présente invention, on peut notamment citer les oxydes métalliques, les carbures métalliques, les oxy-nitrures métalliques, les nitrures métalliques, et leurs mélanges. As fillers which can be used in the context of the present invention, mention may in particular be made of metal oxides, metal carbides, metal oxy-nitrides, metal nitrides, and mixtures thereof.
De préférence, les charges sont choisies parmi l’alumine, le carbure de silicium, la zircone, le carbure de tungstène, le nitrure de bore, le quartz, et leurs mélanges. Avantageusement, les charges utilisées sont les oxydes métalliques, de préférence choisis parmi l’alumine, la zircone, le quartz et leurs mélanges. Préférentiellement, les oxydes métalliques sont de l’alumine. Preferably, the fillers are chosen from alumina, silicon carbide, zirconia, tungsten carbide, boron nitride, quartz, and their mixtures. Advantageously, the fillers used are metal oxides, preferably chosen from alumina, zirconia, quartz and their mixtures. Preferably, the metal oxides are alumina.
Selon un mode de réalisation de la présente invention, la couche de finition comprend de 0,5 à 20% de charges, plus préférentiellement de 1 à 10%, pourcentages exprimés en masse sèche par rapport à la masse sèche totale de la couche de finition. According to one embodiment of the present invention, the finishing layer comprises from 0.5 to 20% of fillers, more preferably from 1 to 10%, percentages expressed in dry mass relative to the total dry mass of the finishing layer .
La taille, et donc le d50, ainsi que la concentration des charges dans la couche de finition peuvent être évaluées en réalisant une observation au microscope optique croisée au microscope électronique à balayage (MEB) muni d’un EDS sur la surface du revêtement selon l’invention. Comme la couche de finition selon l’invention est transparente, il est aisé de voir les charges comprises dans la couche de finition. Une cartographie sur 1 cm2 permet d’obtenir une observation représentative de l’échantillon. La composition chimique de chacune des charges est ensuite déterminée par analyses dispersives en énergie au microscope électronique à balayage (MEB) muni d’un EDS. La distribution en taille des particules est mesurée par traitement informatique et numérique des images. Celle-ci permet de déterminer le d50 ainsi que le volume moyen des charges et donc d’en déterminer la concentration. La concentration volumique des charges peut être calculée à partir du rapport du volume des charges sur la somme du volume des charges et de la couche de finition. La concentration massique est ensuite calculée, en tenant respectivement compte de la masse volumique des charges et de la couche de finition. The size, and therefore the d50, as well as the concentration of the charges in the finishing layer can be evaluated by carrying out an observation with a crossed optical microscope with a scanning electron microscope (SEM) provided with an EDS on the surface of the coating according to l 'invention. As the finishing layer according to the invention is transparent, it is easy to see the fillers included in the finishing layer. A 1 cm 2 mapping provides a representative observation of the sample. The chemical composition of each charge is then determined by energy dispersive analyzes using a scanning electron microscope (SEM) equipped with an EDS. The particle size distribution is measured by computer and digital image processing. This makes it possible to determine the d50 as well as the average volume of the charges and therefore to determine the concentration. The volume concentration of the fillers can be calculated from the ratio of the volume of the fillers to the sum of the volume of the fillers and the top coat. The mass concentration is then calculated, taking account respectively of the density of the fillers and of the finishing layer.
La couche de finition selon l’invention comprend au moins une résine thermostable. Dans le cadre de la présente invention, une résine thermostable est une résine résistante à au moins 200°C. The top coat according to the invention comprises at least one thermostable resin. In the context of the present invention, a thermostable resin is a resin resistant to at least 200 ° C.
Avantageusement, la résine thermostable de la couche de finition est une résine fluorocarbonée, de préférence choisie parmi le polytétrafluoroéthylène (PTFE), les copolymères de tétrafluoroéthylène et de perfluorométhylvinyléther (tels que le MFA), les copolymères de tétrafluoroéthylène et de perfluoropropylvinyléther (tels que le PFA), les copolymères de tétrafluoroéthylène et d'hexafluoropropylène (tels que le FEP) et leurs mélanges. Advantageously, the thermostable resin of the top layer is a fluorocarbon resin, preferably chosen from polytetrafluoroethylene (PTFE), copolymers of tetrafluoroethylene and perfluoromethylvinyl ether (such as MFA), copolymers of tetrafluoroethylene and perfluoropropylvinylether (such as PFA), copolymers of tetrafluoroethylene and hexafluoropropylene (such as FEP) and their mixtures.
Le revêtement antiadhésif selon l’invention peut en outre comprendre au moins une couche de primaire (parfois mentionnée comme « primaire d’accroche » ou « primer »). Cette couche de primaire est destinée à être en contact avec la surface du support de l’article sur lequel le revêtement sera déposé. Avantageusement, cette couche de primaire permet l’accroche du revêtement sur le support. The non-stick coating according to the invention may also comprise at least one layer of primer (sometimes referred to as "bonding primer" or "primer"). This primer layer is intended to be in contact with the surface of the support of the article on which the coating will be deposited. Advantageously, this primer layer allows the coating to hang on the support.
Le revêtement antiadhésif selon l’invention peut également comprendre en outre au moins une couche intermédiaire (parfois mentionnée comme « midcoat ») entre la couche de primaire et la couche de finition. The non-stick coating according to the invention may also further comprise at least one intermediate layer (sometimes referred to as "midcoat") between the primer layer and the top coat.
Le revêtement antiadhésif selon l’invention peut comprendre en outre des attributs, tels qu’un décor ou une fonctionnalité spécifique à l’article comme un indicateur de température optimale de cuisson. Ces attributs sont appliqués entre le primaire et la couche de finition si le revêtement ne comprend pas de couche intermédiaire ou entre la couche intermédiaire et la couche de finition dans le cas contraire. The non-stick coating according to the invention may further comprise attributes, such as a decoration or an article-specific functionality such as an indicator of optimal cooking temperature. These attributes are applied between the primer and the topcoat if the coating does not include an intermediate layer or between the intermediate layer and the topcoat otherwise.
La présente invention a également pour objet un article comprenant un support muni du revêtement antiadhésif selon l’invention. The present invention also relates to an article comprising a support provided with the non-stick coating according to the invention.
Avantageusement, l’article selon l’invention est un article domestique, en particulier un article culinaire. Par article domestique, on entend au sens de la présente invention un objet destiné à assurer les besoins domestiques de la vie courante, en particulier un article destiné à recevoir un traitement thermique ou destiné à produire de la chaleur. En particulier, il peut s’agir d’un article culinaire ou d’un article électroménager. Advantageously, the article according to the invention is a household article, in particular a culinary article. By domestic article is meant within the meaning of the present invention an object intended to ensure the domestic needs of everyday life, in particular an article intended to receive a heat treatment or intended to produce heat. In particular, it can be a culinary item or an appliance item.
Par destiné à recevoir un traitement thermique, on entend au sens de la présente invention un objet qui sera chauffé par un système extérieur de chauffage, en particulier un article culinaire tel que des poêles, des casseroles, des sauteuses, des woks, des crêpières, des faitouts, des marmites, des cocottes, des braisières, des daubières, des grilles de barbecues, des moules à pâtisserie, des caquelons et qui est apte à transmettre l'énergie calorifique apportée par ce système extérieur de chauffage à un matériau ou aliment au contact dudit objet. By intended to receive a heat treatment, is meant within the meaning of the present invention an object which will be heated by an external heating system, in particular a culinary article such as frying pans, pots, sauté pans, woks, crepe makers, pots, pots, casseroles, braising pans, casseroles, barbecue grills, baking molds, fondue pots and which is able to transmit the heat energy provided by this external heating system to a material or food contact of said object.
La présente invention a donc également pour objet un article culinaire comprenant un support muni du revêtement antiadhésif selon l’invention. The present invention therefore also relates to a culinary article comprising a support provided with the non-stick coating according to the invention.
En particulier, l’article culinaire selon l’invention comprend un support qui présente une face intérieure destinée à recevoir des aliments et une face extérieure destinée à être disposée vers une source de chaleur, et un revêtement antiadhésif selon l’invention disposé sur au moins l'une des deux faces du support. In particular, the culinary article according to the invention comprises a support which has an internal face intended to receive food and an external face intended to be disposed towards a heat source, and a non-stick coating according to the invention arranged on at least one of the two faces of the support.
Par destiné à produire de la chaleur, on entend au sens de la présente invention un objet chauffant possédant son propre système de chauffage, en particulier un article électroménager, tel que des fers à repasser, des lisseurs à cheveux, des centrales vapeur ou des appareils électriques destinés à cuisiner comme un saucier. By intended to produce heat, is meant within the meaning of the present invention a heating object having its own heating system, in particular an appliance, such as irons, hair straighteners, steam generators or appliances appliances intended for cooking like a saucer.
Généralement, une partie du support de l’article est revêtue par le revêtement antiadhésif selon l’invention, mais il peut être envisagé que la totalité du support de l’article soit revêtue. Generally, part of the article support is coated with the non-stick coating according to the invention, but it can be envisaged that the entire article support is coated.
D'une manière avantageuse, le support peut être en matériau métallique, en verre, en céramique, en terre cuite ou en plastique. Advantageously, the support can be made of metallic material, glass, ceramic, terracotta or plastic.
De préférence, le support peut être métallique et peut être en aluminium ou alliage d'aluminium, anodisé ou non, éventuellement poli, brossé, sablé ou microbillé, ou en acier éventuellement poli, brossé, sablé ou microbillé, ou en acier inoxydable éventuellement poli, brossé, sablé ou microbillé, ou en fonte d'acier, d'aluminium ou de fer, ou en cuivre éventuellement martelé ou poli. De préférence, le support peut être métallique et peut comprendre une alternance de couches en métal et/ou en alliage métallique, ou est une calotte d'aluminium de fonderie, d'aluminium ou d'alliages d'aluminium doublée d'un fond extérieur en acier inoxydable. Preferably, the support can be metallic and can be made of aluminum or aluminum alloy, anodized or not, optionally polished, brushed, sandblasted or microblasted, or steel possibly polished, brushed, sandblasted or microblasted, or stainless steel possibly polished , brushed, sandblasted or microblasted, or made of cast iron, aluminum or iron, or copper, possibly hammered or polished. Preferably, the support can be metallic and can comprise an alternation of layers of metal and / or metallic alloy, or is a cap of foundry aluminum, aluminum or aluminum alloys lined with an external bottom. Stainless steel.
EXEMPLES EXAMPLES
Dans les exemples et contre-exemples suivants, l’épaisseur moyenne des couches de finition a été évaluée par observations en coupe au microscope électronique à balayage (MEB). La mesure de l’épaisseur des couches de finition a été réalisée en 20 points aléatoires sur les coupes des revêtements. L'épaisseur moyenne des couches de finition a été obtenue en faisant la moyenne de ces 20 mesures. In the following examples and counterexamples, the average thickness of the finishing layers was evaluated by sectional observations using a scanning electron microscope (SEM). The thickness of the finishing layers was measured at 20 random points on the cover sections. The average thickness of the topcoats was obtained by averaging these 20 measurements.
Exemple 1 : Revêtement selon l’invention comprenant une couche de finition contenant des charges d’alumine Example 1: Coating according to the invention comprising a top coat containing alumina fillers
Une formulation de finition a été préparée à partir d’une dispersion de particules de PTFE d’environ 200 nm de diamètre. 2,5% en masse de charges angulaires d’alumine ayant un d50 de 44 pm sous forme de poudre ont été ajoutés à la dispersion. L’extrait sec de la dispersion a été fixé à 50% en masse. Afin de garder ce paramètre fixe, la quantité d’eau a été ajustée. A finishing formulation was prepared from a dispersion of PTFE particles approximately 200 nm in diameter. 2.5% by mass of angular charges of alumina having a d50 of 44 μm in powder form was added to the dispersion. The dry extract of the dispersion was fixed at 50% by mass. In order to keep this parameter fixed, the amount of water has been adjusted.
Cette formulation de finition a été déposée par pistolage sur un article mis en forme (une poêle) revêtu au préalable de deux autres couches toutes majoritairement composées de PTFE : un primaire d’accroche de couleur noire, une couche intermédiaire ainsi que des attributs décoratifs et fonctionnels (décor et indicateur de température optimale de cuisson). La quantité de formulation de finition déposée a été ajustée de manière à obtenir une épaisseur moyenne mesurée de 20 ± 1 pm de la couche de finition après cuisson de l’article pendant 1 1 min à 430°C. This finishing formulation was sprayed on a shaped article (a frying pan) coated beforehand with two other layers all mainly composed of PTFE: a black primer, an intermediate layer as well as decorative attributes and functional (decor and optimal cooking temperature indicator). The quantity of finish formulation deposited was adjusted so as to obtain a measured average thickness of 20 ± 1 μm of the finish layer after baking the article for 11 min at 430 ° C.
On a obtenu après cuisson une concentration de charges de 5% en masse par rapport à la masse totale de la couche de finition (calcul réalisé par rapport à l’extrait sec théorique de la couche de finition). After firing, a concentration of fillers of 5% by mass relative to the total mass of the finishing layer was obtained (calculation carried out with respect to the theoretical dry extract of the finishing layer).
Exemple 2 : Revêtement selon l’invention comprenant une couche de finition contenant des charges d’alumine Example 2 Coating According to the Invention Comprising a Top Coat Containing Alumina Fillers
Une première formulation de finition a été préparée à partir d’une dispersion de particules de PTFE d’environ 200 nm de diamètre. 2,5% en masse de charges angulaires d’alumine ayant un d50 de 44 pm sous forme de poudre ont été ajoutés à la dispersion. L’extrait sec de la dispersion a été fixé à 50% en masse. Afin de garder ce paramètre fixe, la quantité d’eau a été ajustée. A first finishing formulation was prepared from a dispersion of PTFE particles approximately 200 nm in diameter. 2.5% by mass of charges Angular alumina having a d50 of 44 µm in powder form was added to the dispersion. The dry extract of the dispersion was fixed at 50% by mass. In order to keep this parameter fixed, the amount of water has been adjusted.
Cette première formulation de finition a été déposée par pistolage sur un article mis en forme (une poêle) revêtu au préalable de deux autres couches toutes majoritairement composées de PTFE : un primaire d’accroche de couleur noire, une couche intermédiaire ainsi que des attributs décoratifs et fonctionnels (décor et indicateur de température optimale de cuisson). This first finishing formulation was sprayed onto a shaped article (a frying pan) coated beforehand with two other layers, all mainly composed of PTFE: a black primer, an intermediate layer as well as decorative attributes. and functional (decor and optimal cooking temperature indicator).
Une deuxième formulation de finition transparente non-chargée a été préparée à partir d’une dispersion de particules de PTFE d’environ 200 nm de diamètre. L’extrait sec de la dispersion a été fixé à 50% en masse. Afin de garder ce paramètre fixe, la quantité d’eau a été ajustée. Cette deuxième formulation de finition a ensuite été déposée sur la première formulation de finition, par pistolage. A second clear, uncharged topcoat formulation was prepared from a dispersion of PTFE particles approximately 200 nm in diameter. The dry extract of the dispersion was fixed at 50% by mass. In order to keep this parameter fixed, the amount of water has been adjusted. This second finishing formulation was then deposited on the first finishing formulation, by spraying.
La quantité de formulation déposée a été ajustée de manière à obtenir une épaisseur moyenne totale mesurée de 25 ± 1 pm après cuisson de l’article pendant 1 1 min à 430°C et afin que la première formulation représente 40% de la couche de finition et que la deuxième formulation représente 60% de la couche de finition. The quantity of formulation deposited was adjusted so as to obtain a total average thickness measured of 25 ± 1 μm after baking of the article for 11 min at 430 ° C. and so that the first formulation represents 40% of the finishing layer and that the second formulation represents 60% of the top coat.
On a obtenu après cuisson une concentration de charges de 2% en masse par rapport à la masse totale de la couche de finition (calcul réalisé par rapport à l’extrait sec théorique de la couche de finition). After firing, a concentration of fillers of 2% by mass relative to the total mass of the finishing layer was obtained (calculation carried out with respect to the theoretical dry extract of the finishing layer).
Contre-Exemple 1 : Revêtement comprenant une couche de finition non-chargée Une formulation de finition non chargée a été préparée à partir d’une dispersion de particules de PTFE d’environ 200 nm de diamètre. L’extrait sec de la dispersion a été fixé à 50% en masse. Afin de garder ce paramètre fixe, la quantité d’eau a été ajustée. Counterexample 1: Coating comprising an uncharged topcoat An uncharged topcoat was prepared from a dispersion of PTFE particles about 200 nm in diameter. The dry extract of the dispersion was fixed at 50% by mass. In order to keep this parameter fixed, the amount of water has been adjusted.
Cette formulation de finition a été déposée par pistolage sur un article mis en forme (une poêle) revêtu au préalable de deux autres couches toutes majoritairement composées de PTFE : un primaire d’accroche de couleur noire, une couche intermédiaire ainsi que des attributs décoratifs et fonctionnels (décor et indicateur de température optimale de cuisson). La quantité de formulation de finition déposée a été ajustée de manière à obtenir une épaisseur moyenne mesurée de 10 ± 1 pm de la couche de finition après cuisson de l’article pendant 1 1 min à 430°C. This finishing formulation was sprayed onto a shaped article (a frying pan) coated beforehand with two other layers, all mainly composed of PTFE: a black primer, an intermediate layer as well as decorative attributes and functional (decor and optimal cooking temperature indicator). The quantity of finish formulation deposited was adjusted so as to obtain a measured average thickness of 10 ± 1 μm of the finishing layer after baking the article for 11 min at 430 ° C.
Contre-Exemple 2 : Revêtement comprenant une couche de finition contenant des charges d’alumine Counterexample 2: Coating comprising a top coat containing alumina fillers
Une formulation de finition a été préparée à partir d’une dispersion de particules de PTFE d’environ 200 nm de diamètre. 1 % en masse de charges d’alumine colloïdales ayant un d50 de 200 nm ont été ajoutés à la dispersion. L’extrait sec de la dispersion a été fixé à 50% en masse. Afin de garder ce paramètre fixe, la quantité d’eau a été ajustée. A finishing formulation was prepared from a dispersion of PTFE particles approximately 200 nm in diameter. 1% by mass of colloidal alumina fillers having a d50 of 200 nm were added to the dispersion. The dry extract of the dispersion was fixed at 50% by mass. In order to keep this parameter fixed, the amount of water has been adjusted.
Cette formulation de finition a été déposée par pistolage sur un article mis en forme (une poêle) revêtu au préalable de deux autres couches toutes majoritairement composées de PTFE : un primaire d’accroche de couleur noire, une couche intermédiaire ainsi que des attributs décoratifs et fonctionnels (décor et indicateur de température optimale de cuisson). La quantité de formulation de finition déposée a été ajustée de manière à obtenir une épaisseur moyenne mesurée de 20 ± 1 pm de la couche de finition après cuisson de l’article pendant 1 1 min à 430°C. This finishing formulation was sprayed on a shaped article (a frying pan) coated beforehand with two other layers all mainly composed of PTFE: a black primer, an intermediate layer as well as decorative attributes and functional (decor and optimal cooking temperature indicator). The quantity of finish formulation deposited was adjusted so as to obtain a measured average thickness of 20 ± 1 μm of the finish layer after baking the article for 11 min at 430 ° C.
On a obtenu après cuisson une concentration de charges de 2% en masse par rapport à la masse totale de la couche de finition (calcul réalisé par rapport à l’extrait sec théorique de la couche de finition). After firing, a concentration of fillers of 2% by mass relative to the total mass of the finishing layer was obtained (calculation carried out with respect to the theoretical dry extract of the finishing layer).
Contre-Exemple 3 : Revêtement comprenant une couche de finition contenant des charges d’alumine Counter Example 3: Coating comprising a top coat containing alumina fillers
Une formulation de finition a été préparée à partir d’une dispersion de particules de PTFE d’environ 200 nm de diamètre. 2,5% en masse de charges angulaires d’alumine ayant un d50 de 1 pm sous forme de poudre ont été ajoutés à la dispersion. L’extrait sec de la dispersion a été fixé à 50% en masse. Afin de garder ce paramètre fixe, la quantité d’eau a été ajustée. A finishing formulation was prepared from a dispersion of PTFE particles approximately 200 nm in diameter. 2.5% by mass of angular charges of alumina having a d50 of 1 μm in powder form was added to the dispersion. The dry extract of the dispersion was fixed at 50% by mass. In order to keep this parameter fixed, the amount of water has been adjusted.
Cette formulation de finition a été déposée par pistolage sur un article mis en forme (une poêle) revêtu au préalable de deux autres couches toutes majoritairement composées de PTFE : un primaire d’accroche de couleur noire, une couche intermédiaire ainsi que des attributs décoratifs et fonctionnels (décor et indicateur de température optimale de cuisson). La quantité de formulation de finition déposée a été ajustée de manière à obtenir une épaisseur moyenne mesurée de 20 ± 1 pm de la couche de finition après cuisson de l’article pendant 1 1 min à 430°C. This finishing formulation was sprayed onto a shaped article (a frying pan) coated beforehand with two other layers, all mainly composed of PTFE: a black primer, an intermediate layer as well as decorative attributes and functional (decor and optimal cooking temperature indicator). The quantity of finish formulation deposited was adjusted so as to obtain a measured average thickness of 20 ± 1 μm of the finishing layer after baking the article for 11 min at 430 ° C.
On a obtenu après cuisson une concentration de charges de 5% en masse par rapport à la masse totale de la couche de finition (calcul réalisé par rapport à l’extrait sec théorique de la couche de finition). After firing, a concentration of fillers of 5% by mass relative to the total mass of the finishing layer was obtained (calculation carried out with respect to the theoretical dry extract of the finishing layer).
Contre-Exemple 3 bis : Revêtement comprenant une couche de finition contenant des charges d’alumine dont le d50 est 1 ,3 fois supérieur à l’épaisseur de la couche de finition Counter-Example 3a: Coating comprising a top coat containing alumina fillers whose d50 is 1.3 times greater than the thickness of the top layer
Une formulation de finition a été préparée à partir d’une dispersion de particules de PTFE d’environ 200 nm de diamètre. 2,5% en masse de charges angulaires d’alumine ayant un d50 de 26 pm sous forme de poudre ont été ajoutés à la dispersion. L’extrait sec de la dispersion a été fixé à 50% en masse. Afin de garder ce paramètre fixe, la quantité d’eau a été ajustée. A finishing formulation was prepared from a dispersion of PTFE particles approximately 200 nm in diameter. 2.5% by mass of angular charges of alumina having a d50 of 26 μm in powder form was added to the dispersion. The dry extract of the dispersion was fixed at 50% by mass. In order to keep this parameter fixed, the amount of water has been adjusted.
Cette formulation de finition a été déposée par pistolage sur un article mis en forme (une poêle) revêtu au préalable de deux autres couches toutes majoritairement composées de PTFE : un primaire d’accroche de couleur noire, une couche intermédiaire ainsi que des attributs décoratifs et fonctionnels (décor et indicateur de température optimale de cuisson). La quantité de formulation de finition déposée a été ajustée de manière à obtenir une épaisseur moyenne mesurée de 20 ± 1 pm de la couche de finition après cuisson de l’article pendant 1 1 min à 430°C. This finishing formulation was sprayed on a shaped article (a frying pan) coated beforehand with two other layers all mainly composed of PTFE: a black primer, an intermediate layer as well as decorative attributes and functional (decor and optimal cooking temperature indicator). The quantity of finish formulation deposited was adjusted so as to obtain a measured average thickness of 20 ± 1 μm of the finish layer after baking the article for 11 min at 430 ° C.
Le d50 de la charge d’alumine est donc 1 ,3 fois supérieur à l’épaisseur de la couche de finition. The alumina load d50 is therefore 1.3 times greater than the thickness of the top coat.
On a obtenu après cuisson une concentration de charges de 5% en masse par rapport à la masse totale de la couche de finition (calcul réalisé par rapport à l’extrait sec théorique de la couche de finition). After firing, a concentration of fillers of 5% by mass relative to the total mass of the finishing layer was obtained (calculation carried out with respect to the theoretical dry extract of the finishing layer).
Contre-Exemple 5 : Revêtement comprenant une couche de finition contenant des charges d’alumine Counter Example 5: Coating comprising a top coat containing alumina fillers
Une formulation de finition a été préparée à partir d’une dispersion de particules de PTFE d’environ 200 nm de diamètre. 2,5% en masse de charges angulaires d’alumine ayant un d50 de 44 pm sous forme de poudre ont été ajoutés à la dispersion. L’extrait sec de la dispersion a été fixé à 50% en masse. Afin de garder ce paramètre fixe, la quantité d’eau a été ajustée. A finishing formulation was prepared from a dispersion of PTFE particles approximately 200 nm in diameter. 2.5% by mass of angular charges of alumina having a d50 of 44 μm in powder form were added to the dispersion. The dry extract of the dispersion was fixed at 50% by mass. In order to keep this parameter fixed, the amount of water has been adjusted.
Cette formulation de finition a été déposée par pistolage sur un article mis en forme (une poêle) revêtu au préalable de deux autres couches toutes majoritairement composées de PTFE : un primaire d’accroche de couleur noire, une couche intermédiaire ainsi que des attributs décoratifs et fonctionnels (décor et indicateur de température optimale de cuisson). La quantité de formulation de finition déposée a été ajustée de manière à obtenir une épaisseur moyenne mesurée de 40 ± 1 pm de la couche de finition après cuisson de l’article pendant 1 1 min à 430°C. This finishing formulation was sprayed on a shaped article (a frying pan) coated beforehand with two other layers all mainly composed of PTFE: a black primer, an intermediate layer as well as decorative attributes and functional (decor and optimal cooking temperature indicator). The quantity of finish formulation deposited was adjusted so as to obtain a measured average thickness of 40 ± 1 μm of the finish layer after baking the article for 11 min at 430 ° C.
Le d50 de la charge d’alumine est donc 1 ,1 fois supérieur à l’épaisseur de la couche de finition. The alumina load d50 is therefore 1.1 times greater than the thickness of the top coat.
On a obtenu après cuisson une concentration de charges de 5% en masse par rapport à la masse totale de la couche de finition (calcul réalisé par rapport à l’extrait sec théorique de la couche de finition). After firing, a concentration of fillers of 5% by mass relative to the total mass of the finishing layer was obtained (calculation carried out with respect to the theoretical dry extract of the finishing layer).
Contre-Exemple 6 : Revêtement comprenant une couche de finition contenant des charges d’alumine dont le d50 est 3,2 fois supérieur à l’épaisseur de la couche de finition : Counterexample 6: Coating comprising a finishing layer containing alumina fillers whose d50 is 3.2 times greater than the thickness of the finishing layer:
Une formulation de finition a été préparée à partir d’une dispersion de particules de PTFE d’environ 200 nm de diamètre. 2,5% en masse de charges angulaires d’alumine ayant un d50 de 64 pm sous forme de poudre ont été ajoutés à la dispersion. L’extrait sec de la dispersion a été fixé à 50% en masse. Afin de garder ce paramètre fixe, la quantité d’eau a été ajustée. A finishing formulation was prepared from a dispersion of PTFE particles approximately 200 nm in diameter. 2.5% by mass of angular charges of alumina having a d50 of 64 μm in powder form was added to the dispersion. The dry extract of the dispersion was fixed at 50% by mass. In order to keep this parameter fixed, the amount of water has been adjusted.
Cette formulation de finition a été déposée par pistolage sur un article mis en forme (une poêle) revêtu au préalable de deux autres couches toutes majoritairement composées de PTFE : un primaire d’accroche de couleur noire, une couche intermédiaire ainsi que des attributs décoratifs et fonctionnels (décor et indicateur de température optimale de cuisson). La quantité de formulation de finition déposée a été ajustée de manière à obtenir une épaisseur moyenne mesurée de 20 ± 1 pm de la couche de finition après cuisson de l’article pendant 1 1 min à 430°C. Le d50 de la charge d’alumine est donc 3,2 fois supérieur à l’épaisseur de la couche de finition. This finishing formulation was sprayed onto a shaped article (a frying pan) coated beforehand with two other layers, all mainly composed of PTFE: a black primer, an intermediate layer as well as decorative attributes and functional (decor and optimal cooking temperature indicator). The quantity of finish formulation deposited was adjusted so as to obtain a measured average thickness of 20 ± 1 μm of the finish layer after baking the article for 11 min at 430 ° C. The d50 of the alumina filler is therefore 3.2 times greater than the thickness of the finishing layer.
On a obtenu après cuisson une concentration de charges de 5% en masse par rapport à la masse totale de la couche de finition (calcul réalisé par rapport à l’extrait sec théorique de la couche de finition). After firing, a concentration of fillers of 5% by mass relative to the total mass of the finishing layer was obtained (calculation carried out with respect to the theoretical dry extract of the finishing layer).
Résultats Results
- Test à la rayure test anti-adhésivité et coefficient d’usure - Scratch test non-stick test and wear coefficient
Ce test évalue la résistance du revêtement à l’action d’un tampon abrasif appliqué sur sa surface et la chute d’anti-adhérence de ce revêtement par un test de carbonisation au lait après qu’il ait été soumis au cycle d’abrasion. Il est basé sur un test normatif : NF D 21 -51 1 avec des particularités adaptées. This test evaluates the resistance of the coating to the action of an abrasive pad applied to its surface and the drop in non-sticking of this coating by a milk carbonization test after it has been subjected to the abrasion cycle. . It is based on a normative test: NF D 21 -51 1 with specific features.
L’appareil utilisé est un abrasimètre animé d’un mouvement horizontal. Un bras fixe supporte un patin rectangulaire de dimensions 70 ± 5 mm x 30 ± 5 mm, sur lequel est placé un tampon abrasif de même dimension, et comporte une tare permettant l’application d’une charge de 21 N (masse du bras de levier compris). L’abrasif se déplace à la vitesse de 33 allers et retours par minute. La surface abrasée est de 70 mm x 130 mm, soit une course de 100 mm. Au bout de 1000 cycles d’abrasion (soit 1000 allers-retours de l’abrasif), l’évolution de l’anti-adhérence est évaluée après carbonisation d’une pellicule de lait. The device used is an abrasimeter with a horizontal movement. A fixed arm supports a rectangular pad of dimensions 70 ± 5 mm x 30 ± 5 mm, on which is placed an abrasive pad of the same dimension, and includes a tare allowing the application of a load of 21 N (mass of the arm of lever included). The abrasive moves at the speed of 33 back and forth per minute. The abraded surface is 70 mm x 130 mm, i.e. a stroke of 100 mm. After 1000 abrasion cycles (i.e. 1000 round trips of the abrasive), the evolution of the anti-adhesion is evaluated after carbonization of a film of milk.
Le test est stoppé à l’apparition d’une rayure ou une perte d’antiadhésivité (lait accroché de manière irréversible même après nettoyage). The test is stopped at the appearance of a scratch or a loss of non-stick (milk hooked irreversibly even after cleaning).
L’effet des charges dans les revêtements sur leurs performances mécaniques a également été évalué en déterminant l’épaisseur de revêtement éliminée par cycle d’abrasion. Elle se traduit par une vitesse d’abrasion v (ou volume endommagé) décrite par la formule Math 1 dans laquelle (t°) et (tabr) représentent respectivement l’épaisseur du revêtement avant et après abrasion, Sab la surface abrasée et A le nombre de cycles d’abrasion subis (ici 1000 cycles). L’opération est répétée 3 fois par configuration. The effect of loads in coatings on their mechanical performance was also evaluated by determining the thickness of coating removed by abrasion cycle. It results in an abrasion speed v (or damaged volume) described by the formula Math 1 in which (t °) and (t abr ) respectively represent the thickness of the coating before and after abrasion, S ab the abraded surface and A the number of abrasion cycles undergone (here 1000 cycles). The operation is repeated 3 times per configuration.
[Math 1 ] Par la suite, la relation de Schimtz permet de retrouver le coefficient d’usure K (mm3/N.m) et est décrite par la formule Math 2 dans laquelle le volume endommagé [Math 1] Subsequently, the Schimtz relation makes it possible to find the wear coefficient K (mm 3 / Nm) and is described by the formula Math 2 in which the damaged volume
Il p / « He p / "
v est proportionnel à K, au module de la force normale » M'< (21 N) et à la distance parcourue d (soit 200 m). v is proportional to K, to the modulus of the normal force » M '<(21 N) and to the distance traveled d (ie 200 m).
[Math 2] r = K · FK - d [Math 2] r = K · F K - d
- Observation visuelle - Visual observation
Une observation visuelle a été réalisée de chaque article des exemples 1 et 2 et des contre-exemples 1 à 6. L’observation visuelle a été qualifiée de « bonne » dans les cas où les attributs décoratifs et fonctionnels ne sont pas masqués par la couche de finition (pas de perte de détails, pas de perte de couleur) et de « mauvaise » dans les cas contraires. A visual observation was made of each article of examples 1 and 2 and of the counterexamples 1 to 6. The visual observation was qualified as "good" in the cases where the decorative and functional attributes are not masked by the layer finishing (no loss of detail, no loss of color) and "bad" in the contrary cases.
- Transmittance et valeur de Haze totalisée - Transmittance and totalized Haze value
Pour évaluer les propriétés optiques des couches de finition, des mesures ont été réalisées à l’aide d’un Haze-gard i avec la norme ASTM D1003. To assess the optical properties of topcoats, measurements were made using a Haze-gard i with ASTM D1003.
Afin de réaliser ces mesures, les formulations de finition des exemples et contre- exemples ci-dessus ont chacune été appliquées directement sur une plaque émaillée et lisse. La quantité de formulation de finition déposée a été ajustée de manière à obtenir les mêmes épaisseurs moyennes de couche de finition que celles des exemples et contre-exemples, après cuisson de la plaque pendant 1 1 min à 430°C. Les films ainsi obtenus ont été décollés des plaques et analysés. In order to carry out these measurements, the finishing formulations of the above examples and counterexamples were each applied directly to an enameled and smooth plate. The quantity of finish formulation deposited was adjusted so as to obtain the same average thicknesses of finish layer as those of the examples and counterexamples, after baking the plate for 11 min at 430 ° C. The films thus obtained were removed from the plates and analyzed.
Pour être esthétiquement attractif et pour être compatible avec la présence d’attributs décoratifs et fonctionnels (comme par exemple, un décor et/ou un indicateur de température optimale de cuisson), un revêtement doit contenir une couche de finition dont la transmittance directe est supérieure à 90% et dont la valeur de Haze totalisée est inférieure à 40%. To be aesthetically attractive and to be compatible with the presence of decorative and functional attributes (such as, for example, a decor and / or an optimal baking temperature indicator), a coating must contain a top coat with a higher direct transmittance 90% and whose total Haze value is less than 40%.
[Tableau 1 ] [Table 1]
[Tableau 2] [Table 2]

Claims

REVENDICATIONS
1. Revêtement antiadhésif comprenant une couche de finition transparente, ladite couche de finition comprenant au moins une résine thermostable et des charges dont le d50 est au moins 1 ,4 fois supérieur à l’épaisseur moyenne de ladite couche de finition et au maximum 3 fois supérieur à l’épaisseur moyenne de ladite couche de finition, et dans laquelle les charges sont des oxydes métalliques. 1. Non-stick coating comprising a transparent finishing layer, said finishing layer comprising at least one thermostable resin and fillers whose d50 is at least 1.4 times greater than the average thickness of said finishing layer and at most 3 times greater than the average thickness of said top coat, and in which the fillers are metal oxides.
2. Revêtement selon l’une des revendications précédentes, caractérisé en ce que les charges ont un d50 supérieur à 20 pm. 2. Coating according to one of the preceding claims, characterized in that the fillers have a d50 greater than 20 pm.
3. Revêtement selon l’une des revendications précédentes, caractérisé en ce que les charges ont un d50 inférieur à 60 pm. 3. Coating according to one of the preceding claims, characterized in that the fillers have a d50 of less than 60 pm.
4. Revêtement selon l’une des revendications précédentes, caractérisé en ce que la couche de finition comprend de 0,5 à 20% de charges, pourcentages exprimés en masse par rapport à la masse totale de la couche de finition. 4. Coating according to one of the preceding claims, characterized in that the finishing layer comprises from 0.5 to 20% of fillers, percentages expressed by mass relative to the total mass of the finishing layer.
5. Revêtement selon l’une des revendications précédentes, caractérisé en ce que les charges sont des charges minérales présentant une dureté de Mohs supérieure ou égale à 7. 5. Coating according to one of the preceding claims, characterized in that the fillers are mineral fillers having a Mohs hardness greater than or equal to 7.
6. Revêtement selon l’une des revendications précédentes, caractérisé en ce que les oxydes métalliques sont choisis parmi l’alumine, la zircone, le quartz, et leurs mélanges. 6. Coating according to one of the preceding claims, characterized in that the metal oxides are chosen from alumina, zirconia, quartz, and their mixtures.
7. Revêtement selon la revendication 6, caractérisé en ce que les oxydes métalliques sont l’alumine. 7. Coating according to claim 6, characterized in that the metal oxides are alumina.
8. Revêtement selon l’une des revendications précédentes, caractérisé en ce que la couche de finition présente une épaisseur moyenne de 2 à 40 pm, de préférence de 10 à 30 pm. 8. Coating according to one of the preceding claims, characterized in that the finishing layer has an average thickness of 2 to 40 µm, preferably 10 to 30 µm.
9. Revêtement selon l’une des revendications précédentes, caractérisé en ce que ladite résine thermostable est une résine fluorocarbonée, de préférence choisie parmi le polytétrafluoroéthylène (PTFE), les copolymères de tétrafluoroéthylène et de perfluorométhylvinyléther (tels que le MFA), les copolymères de tétrafluoroéthylène et de perfluoropropylvinyléther (tels que le PFA), les copolymères de tétrafluoroéthylène et d'hexafluoropropylène (tels que le FEP) et leurs mélanges. 9. Coating according to one of the preceding claims, characterized in that said thermostable resin is a fluorocarbon resin, preferably chosen among polytetrafluoroethylene (PTFE), copolymers of tetrafluoroethylene and perfluoromethylvinyl ether (such as MFA), copolymers of tetrafluoroethylene and perfluoropropylvinylether (such as PFA), copolymers of tetrafluoroethylene and hexafluoropropylene (such as FH) their mixtures.
10. Article comprenant un support muni du revêtement antiadhésif selon l’une des revendications précédentes. 10. Article comprising a support provided with the non-stick coating according to one of the preceding claims.
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FR3091532A1 (en) 2020-07-10
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US20220112383A1 (en) 2022-04-14
JP2022516959A (en) 2022-03-03
CN113286857A (en) 2021-08-20
BR112021013017A2 (en) 2021-09-14
FR3091532B1 (en) 2022-07-29
WO2020144051A1 (en) 2020-07-16

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