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
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/28—Compounds of silicon
  • C09C1/30—Silicic acid
• • 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
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/28—Compounds of silicon
  • C09C1/30—Silicic acid
  • C09C1/3072—Treatment with macro-molecular organic compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/28—Compounds of silicon
  • C09C1/30—Silicic acid
  • C09C1/3081—Treatment with organo-silicon compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/28—Compounds of silicon
  • C09C1/30—Silicic acid
  • C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/40—Compounds of aluminium
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/40—Compounds of aluminium
  • C09C1/407—Aluminium oxides or hydroxides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
  • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
  • C09C3/10—Treatment with macromolecular organic compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
  • C09C3/12—Treatment with organosilicon compounds
• • 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
  • C09D7/41—Organic pigments; Organic dyes
• • 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
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
  • C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/12—Surface area

Definitions

• Nanocharge of a metal oxide, its synthesis process and its use in a non-stick coating based on fluorocarbon resin generally relates to a nanoparticle (or nanocharge) filler of a metal oxide such as silica, and its use in an aqueous dispersion based on a fluorocarbon resin.
• the present invention also relates to a non-stick coating comprising such a filler, and to a culinary article provided with such a coating.
• the main objective of the present invention is to introduce as finely as possible a charge in the form of nanoparticles of a metal oxide such as silica in non-stick coatings based on fluorocarbon resin, such as for example polytetrafluoroethylene (PTFE) .
• fluorocarbon resin such as for example polytetrafluoroethylene (PTFE)
• PTFE polytetrafluoroethylene
• the fluorocarbon resin-based release coatings are initially prepared from such emulsions, and then are applied to a substrate and sintered.
• a solution known to those skilled in the art consists in improving the compatibility of silica nanoparticles with PTFE by grafting a fluorinated chain, such as for example a poly (HFPO) silane which makes the nanoparticle compatible with PTFE.
• a fluorinated chain such as for example a poly (HFPO) silane which makes the nanoparticle compatible with PTFE.
• a silica modified with a poly (HFPO) silane has the major drawback of being too hydrophobic and can not be used in the PTFE dispersion formulations conventionally used for producing non-stick coatings or impregnation of textiles. Indeed, it is not possible to disperse such a silica in an aqueous medium, and therefore a fortiori in a PTFE emulsion.
• the technical problem that the present invention seeks to solve therefore consists more particularly in making the silica (or any other metal oxide that can be used as a filler in an aqueous dispersion of fluorocarbon resin) compatible with PTFE (therefore hydrophobic), but also dispersible in aqueous medium.
• the applicant has developed a method for synthesizing metal oxide nanoparticles, which comprises not only the grafting of a PTFE-compatible chain (or any other fluorocarbon resin that can be used in the context of the present invention).
• invention for example poly (HFPO) silane, but also the grafting of a second silane-modified polyalkylene glycol chain.
• the two grafts can coexist simultaneously on the same particle, without rejecting one by the other. Indeed one would have expected that once grafted by the hydrophilic or hydrophobic chains, the particle rejects the graft of an opposite nature.
• this nanoburden also has surface-active characteristics which enable it to over-stabilize the PTFE dispersions.
• the present invention relates to a nanocharge of a metal oxide comprising at least two grafted chains, at least one of the chains being hydrophilic and the other being a hydrophobic chain compatible with fluorinated polymers.
• the hydrophobic chain is an oligomer of average molar masses by weight Mw which are between 300 and 20,000 g. mol -1 .
• the weight average molar masses Mw of the hydrophobic chain are between 500 and 10,000 g. mol "1 , and more preferably between 1000 and 5000 g, mol " 1 . Even more preferably, the weight average molar masses Mw of the hydrophobic chain are between 1000 and 1500 g. mol "1 .
• nanoparticle is intended to mean a filler in the form of nanoparticles, one of whose dimensions is between 5 and 2000 nm, preferably between 20 and 200 nm, and better still between 10 and 100 nm.
• metal oxide that may be used in the non-stick coating according to the invention, mention may notably be made of silica, alumina, cerium oxide, zinc oxide, vanadium oxide and zirconium oxide. , titanium dioxide.
• the preferred metal oxide is silica, and especially colloidal silica or fumed silica.
• the hydrophilic chain is a derivative polyalkylene glycol modified with:
• the hydrophilic chain is a derivative of polyethylene glycol (PEG) or a derivative of polypropylene glycol (PFG), and better a derivative of polyethylene glycol (PEG) or polypropylene glycol (PPG) modified with an alkoxysilane (in particular triethoxysilane or trimethoxysilane).
• PEG polyethylene glycol
• PPG polypropylene glycol
• hydrophobic chain according to a first particularly advantageous embodiment of the present invention, it is an oligomer of HFPO modified with an alkoxysilane.
• VDF vinylidene fluoride
• TFE tetrafluoroethylene
• co-oligomers VDF-TFE, VDF-hexafluoropropene, VDF-chlorotrifluoroethylene alone or in mixtures and modified with an alkoxysilane.
• a preferred nanocharge may consist of silica comprising two grafted chains:
• One of the chains being a hydrophilic chain consisting of a polyethylene glycol derivative modified with a triethoxysilane, and
• the other chain being an oligomer of hexafluoropropene oxide (HFPO) modified with a triethoxysilane or a methyldiethoxysilane.
• HFPO hexafluoropropene oxide
• the subject of the present invention is also a dispersion in aqueous phase of at least one fluorocarbon resin comprising a nanofiller according to The invention.
• the fluorocarbon resin used in the dispersion according to the invention may advantageously be chosen from polytetrafluoroethylene (PTFE), the copolymer of tetrafluoroethylene and perfluoropropylvinyl ether (PFA), and the copolymer of tetrafluoroethylene and hexafluoropropene (FEP), polyvinylidene fluoride. (PVDF), MVA (TFE / PMVE copolymer), TFE / PMVE / FAVE terpolymer, ETFE and mixtures thereof.
• PTFE polytetrafluoroethylene
• PFA perfluoropropylvinyl ether
• FEP hexafluoropropene
• PVDF polyvinylidene fluoride
• MVA TFE / PMVE copolymer
• TFE / PMVE / FAVE terpolymer TFE / PMVE / FAVE terpolymer
• ETFE and
• the dispersion according to the invention may comprise, in addition to the fluorocarbon resin and the nanofiller, pigments (for example carbon black, iron oxides, mixed oxides of cobalt and manganese or even titanium dioxide), and or additives selected from thickeners, surfactants, stabilizers and co-solvents.
• pigments for example carbon black, iron oxides, mixed oxides of cobalt and manganese or even titanium dioxide
• additives selected from thickeners, surfactants, stabilizers and co-solvents.
• the present invention also provides a method for synthesizing a silica nanobridge comprising a hydrophilic chain consisting of an alkoxysilane-modified polyalkylene glycol derivative and a hydrophobic chain consisting of a hydrophobic oligomer of HFPO, and / or a VDF and / or an alkoxy silane-modified TFE, said process comprising the following steps:
• the metal oxide is as defined above, and it is the same for the oligomer of functionalized HFPO and modified PEG.
• the grafting is a two-step grafting, in which:
• the grafting of the oligomer of functionalized HFPO on the silica nanobridge is first carried out; then
• the functionalized HFPO oligomer and the modified polyalkylene glycol oligomer are simultaneously grafted onto the silica nanobridge.
• the grafting of the HFPO and PEG oligomers is by amidification of the oligo (HFPO) ester with polyethylene glycol- ⁇ -amines.
• the present invention also relates to a non-stick coating comprising at least one layer comprising at least one fluorocarbon resin alone or in admixture with a heat-stable fixing resin and resistant to at least 200 ° C., this (these) resin (s) forming a continuous sintered network, said non-stick coating being characterized in that it comprises a nanofiller according to the invention.
• Such a non-stick coating has improved properties of corrosion resistance, abrasion resistance and adhesion, as illustrated in the examples.
• the fluorocarbon resin is as defined above.
• the bonding resin may advantageously be chosen from polyamide imides (PAI), polyether imides (PEI), polyamides (PA), polyimides (PI), polyetherketones (PEK), polyetheretherketones (PEEK) and polyethersulfones ( PES), polyphenylene sulfides (PPS), polybenzymidazoles (PBI).
• PAI polyamide imides
• PEI polyether imides
• PA polyamides
• PI polyimides
• PEK polyetherketones
• PEEK polyetheretherketones
• PES polyethersulfones
• PES polyphenylene sulfides
• PBI polybenzymidazoles
• the non-stick coating according to the invention comprises a layer of primer and at least one topcoat, each of which comprises at least one fluorocarbon resin alone or in admixture with a thermostable and resistant to heat-resistant bonding resin. -minus 200 ° C.
• the nanocharge can be indifferently included in one or other of the primer and finish layers, but it is preferably included in the primer layer.
• the subject of the present invention is a culinary article comprising a support having an inner face that can receive food and an outer face intended to be disposed towards the source of heat, characterized in that the inner face is coated with a non-stick coating according to the invention.
• a hollow cap As a support that can be used to produce the culinary article according to the invention, it will be advantageous to use a hollow cap as described above, having a bottom and a side wall rising from the bottom.
• the support used in the context of the present invention may advantageously be made of a material selected from metals, wood, glass, plastics and ceramics.
• aluminum or anodized aluminum supports whether or not anodized, or polished, brushed or micro-blasted aluminum, or polished, brushed stainless steel or aluminum can advantageously be mentioned.
• micro-blasted, or cast iron, or hammered or polished copper It is also possible to mention multilayer composite supports, for example aluminum (or aluminum alloy) / stainless steel bilayer supports and stainless steel / aluminum (or aluminum alloy) / stainless steel tri-layer supports.
• the culinary article according to the invention is produced according to the following method, which comprises the following steps:
• FIG. 1 represents a diagrammatic sectional view of an exemplary culinary article according to the invention, having a coating; nonstick on its inner surface,
• FIG. 2 schematically represents the reaction scheme of the synthesis of the silica nanoburden of Example 1A (channel A) and 1B (channel B).
• FIG. 2 is commented on in the example 1.
• FIG. 1 shows in particular, by way of example of a cooking utensil, a pan 1 with a handle 11, which comprises a hollow metal cap 2 having a bottom 21 and a sidewall 22 rising from the bottom 21.
• the cap 2 has a concave inner surface 201 intended to be placed on the side of the feedable foods, and an outer face 202 intended to be disposed towards a heat source (for example a cooking plate).
• a heat source for example a cooking plate
• the inner face 201 is coated with a non-stick coating 3, which comprises a layer of primer 31 covering the inner face 201, and a topcoat 32 covering the primer layer 31.
• the primer layers 31 and finishing 32 and decor 33 are based on PTFE.
• colloidal silica marketed under the trade name LUDOX AM 30 by the company GRACE DAVISON: it is a colloidal silica that is not surface-modified with a specific surface area of approximately 220 m 2 / g and which is in the form of an aqueous dispersion with a solids content of 30%, the size of the particles is estimated at 50 nm;
• fumed silica marketed under the trade name AEROSIL 150 by the company EVONIK with a specific surface area of about 150m 2 / g in solid form the size of the particles is estimated at 14 nm; monomer: HFPO (97% purity) under the name marketed by ABCR;
• VDF vinylidene fluoride
• pigment flakes (mica and titanium oxide) marketed by Merck under the trade names Iriodin 153 and 225: tests
• the abrasion resistance of a non-stick coating on a sanded aluminum substrate is evaluated.
• 2_5_ means to let soak for 10 minutes and possibly force the start by passing a wet sponge to completely eliminate the film; 0_: means that after the previous process, all or part of the carbonized film remains adherent.
• a grid test is performed according to ISO 2409 followed by immersion of the article for 9 hours (3 cycles of 3 hours in boiling water). Then, it is observed whether or not the non-stick coating has a detachment.
• the quotation is as follows:
• the corrosion resistance of a release coating deposited on an aluminum substrate is evaluated by evaluating its resistance to salt diffusion to the corroding metal substrate. This evaluation is carried out in practice by immersion, for 20 hours, of the substrate coated with the primer layer in a saline aqueous solution brought to a boil. This saline solution comprises 10% by weight of sodium chloride.
• the protocol for this test is that defined in the AFNOR NF D21-511 $ 3.3.5 standard.
• a visual check is made of the final appearance of the coating, which consists in noting the presence or absence of corrosion traces (by visual observation with the naked eye or a binocular magnifying glass). ). This is in practice to detect the presence of traces such as blisters with extensive areas, white traces under the coating. This observation is followed by a grid test according to ISO 2409.
• a fixing PCC1A primer composition comprising the following compounds, their respective amounts being indicated in g per 1000 g of composition:
• a fixing PCC1B primer composition comprising the following compounds, their respective amounts being indicated in g per 1000 g of composition:
• PTFE dispersion (60% solids content): 192 g Dispersion Carbon black (25% solids content): 39 g PAI in aqueous phase + solvent (NMP)
• finishing composition CF1 (colorless and without silica) comprising the following compounds is prepared, their respective quantities being indicated in g per 1000 g of composition:
• Triethanolamine 1.3 g
• this inner surface is sprayed with a thin layer of the CPCIA or CPCIB composition
• the wet primer layer thus formed is then dried at a temperature of about 65 ° C until no longer sticky;
• finishing composition CF1 is then sprayed onto the primer layer;
• composition CPC1B a fumed silica comprising a hydrophobic chain consisting of an oligomer of HFPO.
• HFPO hexafluoropropene oxide
• ring opening anionic polymerization of hexafluoropropene oxide is carried out as follows:
• Hastelloy 100 mL Hastelloy (HC-276) equipped with mechanical agitation, rupture disc, valves and manometer;
• the reactor when the liquid reactants have been introduced, the reactor is cooled by a methanol cooler thanks to its double jacket;
• the autoclave is connected to an external bath and heated to 10 ° C (before heating, the reactor temperature was -20 ° C);
• the polymerization is stopped after 2-3 hours by the addition of 15-20 ml of methanol;
• the aqueous phase is then separated using a dropping funnel and the solvent (in the organic phase) is evaporated by rotary evaporator.
• the resulting product is colorless and viscous.
• the quantitative values are as follows: the reactor is charged with 0.41 g (7.1 mmol) of KF, 2.9 mL (13.2 mmol) of tetraglyme and 10 mL of C 4 F 5 H 5 . Then 45 g (0.27 mol) of hexafluoropropene oxide are transferred into the reactor.
• the polymerization begins when the temperature is close to 0 ° C and is stopped after 2 hours by the addition of 15 ml of methanol.
• the polymer is washed three times with distilled water to remove tetraglyme, methanol and catalyst.
• the solvents are evaporated using a rotary evaporator at 40.degree. 50 ° C. In this case, the yield is 56%, the molar masses are 1290 g / mol by NMR and 1207 by CPV.
• the surface of the fumed silica is hydrolyzed-condensation ("grafting onto") oligomers of hexafluoropropene oxide (HFPO) with an alkoxy -) silane;
• the quantitative values are as follows: 1.0 g of fumed silica, previously dried under vacuum for 2 hours at 200 ° C., is dispersed in a solution of water / ethanol (10/90, 100 ml). This dispersion is then placed under argon with vigorous stirring for 15 minutes. Then 2.6 g (1.7 mmol) of amido (propyl) triethoxysilane functionalized oligo (HFPO) (HFPO x -Si (OEt) 3) are added thereto. The mixture is refluxed for 24 h at 80 ° C., then filtered and washed several times with distilled water. The white powder obtained (Si02-SiO y - x HFPO) is dried in vacuo for 4 h at 80 ° C to constant weight.
• a primer composition identical to the CPC1 composition but by replacing the colloidal silica with a silica nanobond according to the invention comprising a double coating composed of oligomer of HFPO and oligomer of ethylene glycol (PEG).
• the grafting on fumed silica of a "double hair" composed of an Si (OEt) 3 functionalized VDF oligomer and a PEG oligomer functionalized with Si (OEt) 3 is by hydrolysis-condensation.
• the objective is to compatibilize and thus increase the dispersion of colloidal silica in PTFE coatings.
• the silica is modified with the fluorinated chains in a first step under the following conditions: 3.0 g of silica, previously dried under vacuum for 2 hours at 200 ° C., is dispersed in a solution of water / ethanol (10/90, 150mL). This dispersion is then placed under argon with vigorous stirring for 15 minutes. Then 1.26 g (1.8 mmol) of functionalized amido (propyl) triethoxysilane (HFPO3-Si (OEt) 3) oligo (HFPO) are added thereto. The mixture is refluxed for 24 h at 80 ° C., then filtered and washed several times with distilled water.
• HFPO3-Si (OEt) 3 functionalized amido (propyl) triethoxysilane
• the HFPO / PEG ratio is such that the PEG 5 -SiO y- SiO 2 -SiO y -HFPO 3 is in the proportions:
• the contact angle is 86 ° ⁇ 2: this allows in particular to consider an implementation of this silica in the aqueous phase.
• EXAMPLE 1B A Grafting of the Double Hair on Pyrogenic Silica Using Method B (illustrated in FIG. 2)
• the method is similar to the previous one, but the only difference is the simultaneous addition of the two types of hair to modify 1.00 g of silica 0.08 g (0.114 mmol) of HFP0 3 -Si (OEt) 3 and 0.58 g (1.06 mmol) of PEG5-S1 (OEt) 3 ⁇
• the white powder obtained (PEG 5 -SiO there -Si0 2 - SiO y -HFP03) is dried in vacuo for 4 h at 80 ° C.
• a first primer composition according to the invention C1 is then produced by replacing the fumed silica of CPC1B with this doubly grafted silica (according to Example 1A or 1B), with the following quantity, replacement 1/1 / p. Then, one of the faces of the aluminum substrates is conventionally coated with the composition C1 and then the finishing composition CF1 (identical to that used in the comparative example 1).
• Substrates coated with a release coating are obtained in which the doubly grafted silica is in the primer layer. The parts thus obtained are then subjected to the set of tests previously indicated in the present application.
• Example 1 differs from Example 1 in a reduction of the silica content added in the CPC1B type formulation, such that the amount of silica described in Example 1 is in a ratio relative to the fumed silica of 2/1. / p.
• a primer composition identical to the CPC1 composition but by replacing the colloidal silica with a silica nanobridge according to the invention comprising a double coating composed of VDF oligomer and ethylene glycol oligomer (PEG). ).
• the grafting on pyrogenic silica of a "double hair" composed of VDF-Si (OEt) 3 and oligo (PEG) is by hydrolysis-condensation.
• the objective is to compatibilize and thus increase the dispersion of colloidal silica in PTFE coatings.
• VDF Vinyl fluoride
• the autoclave Before the reaction, the autoclave is pressurized to 30 bar of nitrogen to verify the absence of leaks.
• the autoclave is conditioned from various cycles empty (10 ⁇ 2 mbar) / nitrogen to remove any traces of oxygen.
• ditert-butyl peroxydicarbonate as initiator, for example the product marketed under the name Perkadox® 16S by AKZO NOBEL,
• VDF gaseous vinylidene fluoride
• the reactor is gradually heated stepwise to the following temperatures 40 ° C (about 10 minutes), 50 ° C (about 20 minutes), and finally 60 ° C (4 hours). At 60 ° C, the pressure is 19 bar, then it drops to 1 bar after 4 hours of heating at this temperature.
• oligomers in the form of powder are obtained, while the filtrate (which contains telomeres of lower molar masses) is evaporated and then dried.
• the reaction mixture is heated for 4 hours at 74 ° C. After cooling, the triethoxysilane-modified PVDF oligomer is precipitated in dry pentane and filtered, and then dried.
• the NMR spectra of 1 R and 19 F show the characteristic signals of the VDF units and of the CH 2 CHISi (OEt) 3 end:
• Example 3A a grafting of the double hair on pyrogenic silica by method A (illustrated in Figure 2).
• the silica is modified with fluorinated chains in a first step with the following conditions: 3.0 g of silica, previously dried under vacuum for 2 hours at 200 ° C., is dispersed in a solution of water / ethanol (10/90, 150mL).
• the mixture is refluxed for 24 hours at 80 ° C, then filtered and washed several times with distilled water.
• the white powder obtained (SiO 2 -SiO y -VDFx) is dried under vacuum for 4 hours at 80 ° C. lg (1.8 mmol) of PEG 9 -S1 (OEt) 3) was then grafted onto the surface of the silica using the same synthetic method.
• VDF / PEG ratio is such that PEG 5 -SiO y -SiO 2 -SiO y -VDF 3 is in the proportions:
• This rate is optimized: it makes it possible to reduce the hydrophobicity of the silica compared with Comparative Example 2.
• the contact angle is 86 ° ⁇ 2: this allows in particular to consider an implementation of this silica in the aqueous phase.
• EXAMPLE 3B Grafting of the Double Hair on Pyrogenic Silica by Method B (illustrated in FIG. 2)
• the method is similar to the previous one, but the only difference is the simultaneous addition of the two types of hair to modify 1.00 g of silica 0.08 g (0.114 mmol) of PVDF-Si (OEt) 3 and 0.58 g (1.06 mmol) of PEG5-S1 (OEt) 3 ⁇
• the white powder obtained (PEG 5 -SiO there -Si0 2 - SiO y -HFP03) is dried in vacuo for 4 h at 80 ° C.
• a primer composition according to the invention C3 is then produced by replacing the fumed silica of CPCIB with this doubly grafted silica (according to Example 3A or 3B), with the following quantity, replacement 1/1 / p.
• one of the faces of the aluminum substrates is conventionally coated with the composition C1 and then the finishing composition CF1 (identical to that used in the comparative example 1).
• Substrates coated with a non-stick coating are obtained in which the doubly grafted silica is found in the primer layer. The parts thus obtained are then subjected to the set of tests previously indicated in the present application.
• EXAMPLE 4 This example differs from Example IA by an increase in the size of the nanoparticles, which is here of the order of 1200 nm.

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