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
  • 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
• • 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
• • 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
• • 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
• • 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
  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers

Definitions

• the present invention relates to a release liner having improved scratch resistance.
• the release coatings commonly used for coating cookware are obtained from compositions based on fluorocarbon resin, for example based on polytetrafluoroethylene (PTFE), deposited on a metal support.
• fluorocarbon resin for example based on polytetrafluoroethylene (PTFE)
• PTFE polytetrafluoroethylene
• Such PTFE-based coatings known for their anti-adhesive properties as well as for their chemical and thermal resistance, however, have the drawback of being particularly sensitive to scratching. Also, repeated uses cause a decrease in the non-stick properties of such coatings and lead to premature wear of the cookware with this type of coatings.
• a widespread technique consists in applying, directly to the metal support, a so-called “hard” underlayer, prior to the application of at least one fluorocarbon resin-based primer and then one or more topcoats. , also based on fluorocarbon resin.
• This "hard” underlayer forms a barrier preventing scratches from reaching the metal support.
• Various types of underlays have thus been used, among which there may be mentioned sub-layers consisting of alumina, enamel, stainless steel or polyamide imide resin (PAI).
• composition of the underlayer described in EP 1 169 141 is constituted, after baking, exclusively PEEK.
• composition of the underlayer described in EP 1 169 142 for its part comprises, after firing, at least 50% by weight of PEEK, the remainder being composed of pure thermostable polymers or in a mixture, such as a polyisulfide of phenylene (PPS), a polyetherimide (PEI), a polyimide, a polyetherketone (PEK), a polyethersulfone (PES) or a polyamide imide (PAI), and inert fillers such as metal oxides, silica, particles mica or lamellar fillers.
• PPS polyisulfide of phenylene
• PEI polyetherimide
• PEK polyetherketone
• PAI polyamide imide
• inert fillers such as metal oxides, silica, particles mica or lamellar fillers.
• release coatings comprising the application of an underlayer formed exclusively or predominantly of PEEK.
• the underlayer is formed exclusively or predominantly of PEEK
• the cost of manufacture is further greatly increased, the PEEK being a particularly expensive resin.
• the problem is therefore to achieve a release coating which has very good performance in terms of scratch resistance, which retains its anti-adhesion properties over time and that overcomes all the disadvantages mentioned above in the implementation of the manufacturing process, the choice of raw materials used and the economic impact that this entails.
• a solution to the problem posed is a release coating comprising at least a first primary layer applied to a metal support and covered by one or more fluorocarbon resin-based topcoats.
• the first primary layer comprises, as a percentage of dry matter measured on the total composition, from 9 to 15% by weight of a fluorocarbon resin, from 4 to 5% by weight of a polyamide imide resin (PAI ), from 0.12 to 1.1% by weight of a polyetheretherketone resin (PEEK), the remainder being technological additives, inert fillers such as pigments, and dispersive media.
• a fluorocarbon resin from 9 to 15% by weight of a fluorocarbon resin, from 4 to 5% by weight of a polyamide imide resin (PAI ), from 0.12 to 1.1% by weight of a polyetheretherketone resin (PEEK), the remainder being technological additives, inert fillers such as pigments, and dispersive media.
• PAI polyamide imide resin
• PEEK polyetheretherketone resin
• the Applicant has found, surprisingly and unpredictably, that the incorporation of a very small amount of PEEK, within a given range of selected weight percentages, in the composition of a first primer layer made it possible to obtain a coating final anti-adhesive having excellent scratch resistance, contrary to previous teachings recommending the implementation of an underlayer comprising at least 50% by weight of PEEK.
• the present invention also relates to a culinary article coated with a non-stick coating as described above and will be detailed in the following description.
• the non-stick coating according to the invention can be deposited on any metal support resistant to temperatures above 400 ° C.
• This metal support may for example be aluminum, aluminum alloy, stainless steel or titanium.
• this support can be left smooth or made slightly rough, especially by sandblasting.
• a first primary layer according to the invention is applied to this metal support, comprising, as a percentage of dry matter, measured on the total composition of said first primary layer, from 9 to 15% by weight of a fluorocarbon resin, from 4 to 5% by weight of a polyamide imide resin (PAI), from 0.12 to 1.1% by weight of PEEK, the remainder being technological additives, inert fillers such as pigments, and dispersive media.
• a fluorocarbon resin from 4 to 5% by weight of a polyamide imide resin (PAI)
• PAI polyamide imide resin
• PEEK polyamide imide resin
• weight contents mentioned above correspond to the respective amounts of fluorocarbon resins, PAI and PEEK in the form of pure product, in the event that each of them is introduced into the composition of the first primary layer at 100% solids content.
• most of the said resins are generally used in the form of a dispersion, for example an aqueous dispersion.
• composition A of primary first layer according to the invention is as follows:
• aqueous dispersion of PTFE (60% solids) 15 to 25% - Aqueous dispersion of PAI (10% solids) 40 to 55% - PEEK (pure product) 0.12 to 1 , 10% - aqueous dispersion of colloidal silica (30% solids) 15 to 25% - aqueous dispersion of carbon black (at 20% solids) of 3.0 to 4.5% - technological additives of 10 to 24% - dispersive media of 54 to 80%.
• a polyetheretherketone resin (PEEK) having a suitable particle size, which does not lead to the formation of a first rough primary layer, will preferably be used.
• a particle size of PEEK of between 5 and 35 ⁇ m is more particularly preferred.
• the composition of the first primary layer indicated above comprises an adhesion agent which is, in this case, colloidal silica and a pigment, carbon black. .
• composition of the first primary layer comprises technological additives as well as dispersive media which, together, make it possible to adapt the formulation of the composition to the mode of application thereof.
• the dispersive media currently used are aqueous media, such as, for example, a base and / or water, or organic solvents, or even mixtures of aqueous media and organic solvents.
• the application of the first primary layer can be done by any conventional method commonly used for the application of fluorocarbon resin-based layers.
• it will implement a spray application, which allows, among other things, to obtain a first continuous primary layer and having no surface defect.
• compositions of first primary layer detailed in the present description are adapted to said spray application.
• Such technological additives for screen printing application may comprise one or more of the following compounds: a solvent, a thickening agent and / or a gelling agent and an antifoam agent to obtain a smooth and homogeneous layer.
• the antifoaming agent is for example chosen from mineral oils or silicones.
• the thickness of the first primary layer is between 4 and 12 ⁇ r ⁇ , preferably between 4 and 8 ⁇ m.
• the release coating according to the invention comprises a second primary layer deposited on the first primary layer and prior to the application of each of the fluorocarbon resin-based finishing layers.
• this second primary layer comprises a fluorocarbon resin and a polyamide imide resin (PAI).
• PAI polyamide imide resin
• the second primary layer may further comprise a polyetheretherketone resin (PEEK).
• PEEK polyetheretherketone resin
• a second primary layer that does not contain any resin.
• PEEK polyetheretherketone
• the second primary layer has the following composition, the weight contents of the resins being, as above for the composition of the first primary layer, expressed in percentages of pure product:
• fluorocarbon resin - PAI resin from 1.5 to 2.0% - aqueous dispersion of colloidal silica from 3 to 6% - aqueous dispersion of carbon black from 0.6 to 1.0% - technological additives from 12 to 22% - dispersive media from 39 to 58%.
• the compounds which can be used as technological additives and dispersive media, as well as their respective roles, are of the same nature as those indicated above for the composition of the first primary layer.
• a particular composition B of second primary layer devoid of PEEK and prepared from an aqueous dispersion of the resins may be the following:
• aqueous dispersion of PTFE (60% solids content) of 30 to 40% - aqueous PFA dispersion (at 50% solids content) of 8 to 12% - aqueous PAI dispersion (at 10% of extract dry) from 15 to 20% - aqueous dispersion of colloidal silica (at 30% solids content) of 10 to 20% - aqueous dispersion of carbon black (at 20% solids content) of 3.0 to 5, 0% - technological additives from 12 to 22% - dispersive media from 39 to 58%.
• composition of second primary layer devoid of PEEK for producing an anti-adhesive coating according to the invention is the composition of the primary layer explained in EP 1 169 141 and EP 1 169 142.
• the application of the second primary layer can also be done by any conventional method commonly used for the application of fluorocarbon resin-based layers and, in particular, by spraying.
• the thickness of the second primary layer is between 4 and 12 ⁇ m, preferably between 4 and 8 ⁇ m.
• the application is made of at least one fluorocarbon resin-based topcoat.
• Fluorocarbon resins that may be suitable for the composition of the first and second primary layers and topcoats are described in particular in US 5,536,583.
• the fluorocarbon resin of the first primary layer and, when it exists, the second primary layer comprises at least one compound chosen from polytetrafluoroethylene (PTFE), the copolymer of tetrafluoroethylene and perfluoropropylvinylether (PFA) or the copolymer tetrafluoroethylene and hexafluoropropylene (FEP).
• PTFE polytetrafluoroethylene
• PFA perfluoropropylvinylether
• FEP hexafluoropropylene
• two finishing layers will be deposited, first an intermediate finishing layer and then an upper finishing layer.
• aqueous dispersion of PTFE (60% solids content) of 70 to 85% - aqueous dispersion of PFA (at 50% solids content) of 0.1 to 1.0% - aqueous dispersion of carbon black (at 20% solids content) from 0.01 to 0.05% - technological additives + dispersive media from 11 to 28% - TiO 2 coated mica flakes from 0.1 to 0 , 4%.
• EP 1 169 141 and EP 1 169 142 describe other compositions of intermediate and upper finishing layers that can be used in the context of the present invention.
• first and second primers and topcoats After application of these finishes, one proceeds to sintering the assembly of first and second primers and topcoats, for example at a temperature of 400-420 0 C for 3 to 7 minutes.
• the total thickness of the two intermediate and top finishing layers is between 12 and 25 ⁇ m.
• Tests were then carried out to determine the anti-blocking properties as well as the scratch resistance of the non-stick coatings according to the invention. Test 1
• This test 1 consists in carrying out intensive cooking of food representing 1 to 2 years of use, either using metal spatulas to turn the food and cook them, or using a metal whisk to cook the food. food.
• the second comprising a "hard" sub-layer based on PAI, first and second primary layers of composition also in accordance with composition B, and
• the third having no hard underlayer but a first primary layer of a composition according to composition A indicated above and a second primary layer according to composition B.
• the intermediate and top finishing layers were identical for these three coatings and compositions respectively complying with the compositions C and D indicated above.
• This test consists in determining the scratch resistance of cookware covered with anti-adhesive coatings.
• This test implements a device for simulating an attack by a metal utensil, such as a canopy, of the non-stick surface of a culinary article.
• the axis of the support of the balls makes 100 rotations in 2'36 '' while the arm which supports the axis of the balls is animated with a speed of rotation of 100 turns in 8'10 ''.
• the temperature of the surface is maintained around a temperature of 180 ° C, the weight of the entire stripe device comprising the three balls being fixed at 310 g ⁇ 5 g.
• the decrease in anti-adhesion performance of the release coating is measured by the so-called "carbonized milk” method recorded under standard NF 21-511.
• the performance of one antiblocking raised is determined by the measured time at which the film of carbonized milk not detached completely from the cooking surface.
• the present test 2 was carried out on a plurality of stoves all comprising an aluminum metal support coated with a non-stick coating according to the invention and comprising a first primary layer of composition A, a second primary layer of composition B, an intermediate topcoat of composition C and an upper topcoat of composition D, compositions B, C and D being identical in all the release coatings tested, only the weight content of PEEK varying in composition A of the first primary layer.
• the pan is then placed at a 135 ° angle under a jet of cold water and the behavior of the carbonized milk film is observed.
• the first primary layer comprises from 0.12 to less than 1.2% by weight, advantageously from 0.12 to 1.0% by weight, and more preferably from 0.12 to 0.9% by weight. by weight, PEEK, anti-adhesion character is very much improved, since deteriorates only after 3 hours 15 test or even after 4 hours and even 4 hours 15.
• a first primary layer comprising low weight contents of PEEK, and in particular PEEK contents of less than or equal to 0.06% by weight, does not make it possible to improve the scratch resistance time of the non-stick coating, the anti-adhesion character being lost after 2:30 - 2:45, as in the case of a composition A devoid of PEEK.
• composition A for a content of 1.68% by weight of PEEK in composition A, the inventors have observed difficulties in applying composition A, the final coating obtained being also very rough and, therefore difficult to exploit (results indicated by (*) in the table).
• mineral fillers such as pigments, such as a sodium silico-aluminate or ultramarine pigment, enamel frit and quartz, and an organic load, namely low polyphenylene sulphide (PPS) levels.
• PPS polyphenylene sulphide
• the scratch resistance times obtained in the context of the present test 2 are at most 2 hours 45 min. those obtained with non-stick coatings comprising a first primary layer having PEEK contents of between 0.12 and 1.1%.

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• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Food Science & Technology (AREA)
• Organic Chemistry (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Laminated Bodies (AREA)
• Paints Or Removers (AREA)
• Cookers (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Food-Manufacturing Devices (AREA)

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• 2004
  • 2004-06-02 FR FR0405964A patent/FR2871038B1/fr not_active Expired - Fee Related
• 2005
  • 2005-05-31 KR KR1020067027468A patent/KR20070035007A/ko not_active Application Discontinuation
  • 2005-05-31 EP EP05775546A patent/EP1753546A1/fr not_active Withdrawn
  • 2005-05-31 US US11/628,384 patent/US20080131703A1/en not_active Abandoned
  • 2005-05-31 BR BRPI0511762-3A patent/BRPI0511762A/pt not_active IP Right Cessation
  • 2005-05-31 JP JP2007514024A patent/JP2008501501A/ja active Pending
  • 2005-05-31 WO PCT/FR2005/001334 patent/WO2006000685A1/fr active Application Filing
  • 2005-05-31 CN CNA2005800182757A patent/CN1976764A/zh active Pending
  • 2005-05-31 RU RU2006143631A patent/RU2359762C2/ru not_active IP Right Cessation

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