• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to an aqueous composition comprising a polyimide a polyamide imide or polyamide-amic acid, a Lewis base, a polar aprotic solvent, with at least 15% water relative to the total weight of said composition, characterized in that the Lewis base is an aminosilane or silazane. The present invention also relates to a process for preparing such a composition, as well as to a method of manufacturing an article comprising a metal substrate to which such a composition is applied.
    公开号:FR3015507A1
    申请号:FR1363355
    申请日:2013-12-20
    公开日:2015-06-26
    发明作者:Barbara Gantillon；Jean-Luc Perillon
    申请人:SEB SA；
    IPC主号:
    专利说明:

    [0001] Aqueous compositions for primary non-stick coatings and process for their preparation
    [0002] The present invention generally relates to aqueous compositions for fluorocarbon resin-based non-stick coating primers. The present invention also relates to a process for the preparation of such a composition, a nonstick coating primer composition incorporating such a composition, and a method of manufacturing an article comprising a metal substrate to which such a composition is applied. primary. Non-stick PTFE coatings are widely used in the field of cookware. They are made from at least one layer containing the perfluorinated resin and a tackifying resin. This primary layer is then coated with one or more layers of PTFE in which the amount of PTFE is gradually increased. The adhesion resins allowing adhesion of this primer and other fluoride layers on the support are generally of PAI, PPS, PES, PEEK type. In the particular case where light-colored primers are desired, PES, PPS or PEEK are preferred. However, the use of these resins is not easy because they are not very soluble other than in polar aprotic solvents, which are for the most part subject to labeling as a harmful or even toxic product in the REACH regulation. . These resins are in practice used in powder form. Moreover obtaining small particle size powders is difficult and expensive which makes it difficult to grind these polymers to a dimension less than D50 equal to 10 μm. It follows that the distribution of these resins in the primer layer is not homogeneous and leads to loss of adhesion to use. From this point of view, the PAI resins which are delivered in solution or in water-dilutable powder are easier to implement. However, they incorporate large amounts of solvent. The need to use polar aprotic solvents (NEP, NMP, DMEU) leads to significant environmental and health impacts. When delivered in water-dilutable powder, the solvent stress is overcome, but these PAI resins also show a thermal stability which is considered insufficient. Indeed during the sintering step of PTFE (carried out at over 370 ° C and preferably at 415 ° C), a small fraction of PAI decomposes even if it does not affect most properties. In addition, the use of a labile amine for carrying out the PAI resin in aqueous phase leads to the generation of a proportion of volatile organic compounds which is no longer negligible when working in an aqueous medium, which induces a unacceptable yellowing of the coating. On the other hand, the preparation of silica grafted with polyamic acids is known (Peng Liu, Iranian Polymer Journal 14, (11) 2005, 968-972). These grafted silicas actually have improved temperature stability, but on the one hand the starting compound is an already existing silica, on the other hand all the modifications are carried out in a solvent medium and their use is suggested (see conclusion) in solvent media which does not solve the environmental constraints.
    [0003] EP 0386379 and FR 2625450 of Corning Glass Works both describe, in a similar manner, mixtures of PAI and an aminosilane. In the procedure described, the amino silane is mixed with the precursor of PAI already in aqueous solution, that is to say that it already incorporates an amine for salification and given the choice of PAI described in Examples, a solvent, this solvent is necessary for carrying out the mixture in liquid form. These patents are not exempt from the presence of the volatile amine capable of generating yellowing or the presence of a potentially toxic polar aprotic solvent. To overcome these drawbacks, the Applicant has developed an aqueous composition based on polyimide or polyamide imide or polyamide-amic acid, containing an aminosilane or a silazane. The use of an amino silane or a silazane makes it possible to obtain a polyamide-amide polyelectrolyte emulsified in water without using very nucleophilic compounds such as the amines which lead to oxidation and formation. very yellowing coatings. In addition to the decrease in yellowing other properties are substantially improved. This also makes it possible to create a hybrid by "overcreating the PAI resin" via silanols. This is possible because the aminosilane is somehow pre-prepared on the chain. Additionally, it also makes it possible to improve the resistance to abrasion by generating in the formula nanodomaines of silica obtained by the condensation of the silanols with each other. This also provides a significantly enhanced thermal stability of the nanocharged polymer film. A thermal stability can for example be measured by observing the shift of the glass transition temperature of at least 20 ° C and a shift of the thermal degradation curve under nitrogen of at least 40 ° C between a semi product. as a standard and a semi-finished product according to the process. This nanocharged PAI film has good adhesion to the metal substrate which is greatly improved due to the coupling of a portion of the silanols with the metal support.
    [0004] The polymer such as PAI, and more particularly in the case of a polyamide amino acid contains many reactive terminations, in particular such as carboxylic groups and amides which will be able to react with the nitrogenous reactive group of the amino-silane or silazane. The PAI in solution in a polar aprotic type solvent (CIP, NMP, DMEU, DMSO etc.) or in the form of a wet powder in water is emulsified in water by reaction with the aminosilane or silazane . In this process, the amino-silane or silazane groups are and NH. Aminosilanes graft via their termination, respectively NH2 is also possible that some of them can be grafted directly to the polyamide alkoxy groups (methoxy or ethoxy or silanols). When the amic acid solution by their in the form of aqueous is carried out and taking into account the local acidity of the medium by the presence of still free carboxylic groups, hydrolysis of the alkoxysilane groups to silanol is observed which further strengthens the compatibilization with water. If necessary, the formulation is completed with an alkoxysilane mixture. During the steaming of the composition and after evaporation of the water and alcohols, the crosslinking of the whole is obtained by a sol-gel type condensation reaction which creates a network of silica nanofillers in the organic PAI matrix and by cyclization of the imide groups. This makes it possible to obtain an organic-inorganic hybrid structure with the formation of a perfectly dispersed silica network of nanometric size in the PAI matrix. The present invention therefore more particularly relates to an aqueous composition comprising a polyimide polyamide imide or polyamide-amic acid, a Lewis base, a polar aprotic solvent, with at least 15% water relative to the total weight of said composition characterized in that the Lewis base is an aminosilane or a silazane.
    [0005] Advantageously, the aminosilane or the silazane are present in said composition in a proportion of 0.1 to 10% by weight of said composition. Advantageously, the aminosilane is 3-amino-5 propyltriethoxysilane (APTES). Advantageously, silazane is hexamethyldisilazane. Advantageously, the polar aprotic solvent is present in a proportion of 1 to 70% by weight relative to the total weight of the composition. Advantageously, the polar aprotic solvent is N-ethyl morpholine. Another subject of the present invention is a non-stick coating primer composition comprising an aqueous composition according to the invention as defined above and a fluorocarbon resin dispersion. The fluorocarbon resin may be selected from the group consisting of polytetrafluoroethylenes (PTFE), copolymers of tetrafluoroethylene and perfluoropropylvinylether (PFA), copolymers of tetrafluoroethylene and hexafluoropropene (FEP), polyvinylidene fluorides (PVDF), MVA (TFE / PMVE copolymer), TFE / PMVE / FAVE terpolymers, ETFE, and mixtures thereof. Polytetrafluoroethylene (PTFE), or a mixture (PTFE / PFA) of polytetrafluoroethylene (PTFE) and copolymer of tetrafluoroethylene and perfluoropropylvinylether (PFA), or a mixture (PTFE / FEP) of polytetrafluoroethylene (PTFE) and copolymer of tetrafluoroethylene and hexafluoropropene (FEP). The present invention further relates to a process for the preparation of a non-stick coating primer composition comprising the following steps: a polyimide or polyamide imide or polyamide-amic acid polymer is dissolved in a polar aprotic solvent for forming a homogeneous mixture - is introduced into said mixture a Lewis base to fix it on said polymer; water is added to the mixture thus formed; optionally, a second Lewis base, which is neither a silane nor a silazane, is added to said mixture; the fluorocarbon dispersion is added; and optionally additionally said charges and / or pigments are added to said mixture. The present invention further relates to a method of manufacturing an article comprising the following steps - providing a metal substrate having two opposite faces; - applying to one of the faces of said substrate at least one layer of primer composition - the application on said primer composition layer of at least one topcoat layer comprising at least one fluorocarbon resin; then - cooking the assembly at a temperature between 370 ° C and 430 ° C. Finally, another subject of the present invention is an article capable of being obtained according to the article manufacturing method according to the invention. It will be for example a culinary article one of whose faces constitutes an internal face intended to be in contact with food placed inside said article and the other side is a convex external face intended to be in Contact with a heat source.
    [0006] EXAMPLES Tests Determination of the dry extract of an aqueous semi-finished mixture PRINCIPLE The dry extract of a product is the residual solid part remaining after evaporation of the volatile matter it contains. The temperature and the drying time play a large role, since the high-boiling solvents, the monomer fractions, the reactive diluents and the reaction by-products (depending on their degree of retention) leave the film very slowly. training. It is therefore very important to define in a very conventional way standardized drying conditions, as close as possible to the practice.
    [0007] OPERATIVE PROCEDURE To measure this dry extract, proceed as follows: - we weigh an aluminum cup: mo = mass of the cup; - There is between 0.5g and 3g of product to study: - Weigh the filled cup: m1 = cup mass filled - ml-mo = mass of the sample before baking the - we place the cup in an oven at 210 ° C for two hours; after steaming and after cooling, the cup is weighed: mass m2; - m2-m0 = mass of the sample after steaming; the dry extract is given by formula (1) below: Dry extract = 100 × (m 2 -m 0) / Evaluation of the stability of the viscosity of an aqueous semi-finished mixture or a composition of primer in aqueous phase The aim is to evaluate the viscosity stability of an aqueous semi-finished (PTFE-free) or primer (with PTFE and fillers) mixture applied by spraying by measuring the flow times according to DIN EN ISO 2433 / ASTM D5125 by means of section 2.5 or section 4: - the viscosity corresponds to the continuous flow time expressed in seconds of the volume of the section through the calibrated orifice . The choice of the cut is made according to the supposed viscosity of the product. - Monitoring the evolution of the viscosity by measuring the continuous flow time of the normalized volume and at room temperature immediately after the preparation of the compositions, and monitoring the evolution of this viscosity over time at room temperature; - Put in oven at 40 ° C of the compositions once formulated; then followed in the course of the evolution of the flow time and hence the viscosity (evaluation of the stability of the emulsion after aging at 40 ° C.) Procedure and method In a reactor, the PAI is introduced which can be either in the form of a wet powder (polyamic acid, PAA, with a hydroxyl number of between 40 and 200 meq KOH / g), or in the form of a PAI polymer in solution in a polar aprotic solvent. Preferably, in the case where the PAI is in the form of a powder, it is solubilized in a polar aprotic solvent, preferably non-toxic or even unclassified.
    [0008] The neutralization reaction of the terminal acid groups PAI or PAA with the amine function of the aminosilane leads to the implementation in the aqueous phase or water + solvent of the PAI resin. Under these conditions, the condensation of the silanol groups on themselves is reduced. In this manner, an alkoxysilane is chemically grafted onto a PAI resin. Then in the next phase, alkoxysilane groups are progressively hydrolyzed to hydroxyl groups, silanols, which by condensation during firing form a nanostructured network of silica within the polymer matrix. The resin thus dispersed in aqueous phase or in water mixed with a co-solvent can be used as such in the fluorinated primary formulations.
    [0009] This mixture remains stable despite the alkalinity of the PTFE dispersion, the condensation of silanols generating an inorganic phase very finely dispersed and more or less related to the matrix PAI being observed only during cooking.
    [0010] COMPARATIVE EXAMPLE 1 SEMI-FINISH SF1 Preparation of an aqueous mixture based on PAI (powder) and triethylamine. An aqueous semi-finished mixture is prepared comprising the following compounds, their respective amounts being indicated in g for: polyamide amino acid (at 35% solids content): 103 g; triethylamine: 21.4 g; demineralized water : 485 g, TOTAL: 609.4 g To prepare the semi-finished aqueous mixture, the following procedure is carried out: a mixture of water and triethylamine is introduced into a reactor; the resulting mixture is stirred, then heated to 65 ° C +/- 5 ° C; Then, stirring the polyamide amic acid powder is introduced into the mixture; the mixture thus obtained is stirred at 65 ° C. for a minimum of 5 hours up to a maximum of 10 hours. The properties of the aqueous mixture thus obtained are the following: - theoretical solids content: 6%, - solids content measured in the solution: 6.3%, - this is a honey-colored translucent product, viscous, - Viscosity (in cross-section) 4 according to DIN EN ISO 2433 / ASTM D5125): 50 sec, - after aging at 40 ° C, the product forms a gel after only 10 days of storage (no flow, non-measurable viscosity). COMPARATIVE EXAMPLE 2 Preparation of an aqueous mixture of PAI (powder), triethylamine and colloidal silica. The silica content of this solution gives a final rate on the dry film of 11.6%. An aqueous semi-finished mixture is prepared comprising the following compounds, their respective amounts being indicated in g for: polyamide amino acid (at 35% solids content): 103 g; triethylamine: 21.4 g; demineralized water 485 g, 30 - Colloidal silica (30% solids): 16 g - TOTAL: 625.4 g To prepare the semi-finished aqueous mixture, the following procedure is carried out: a mixture of water and triethylamine; the resulting mixture is stirred, then heated to 65 ° C +/- 5 ° C; then, with stirring, the polyamide amic acid powder is introduced into the mixture; the resulting mixture is stirred at 65 ° C for a minimum of 5 hours up to a maximum of 10 hours; The solution is allowed to cool and a colloidal silica dispersion of size of the order of 40 to 200 nm is introduced at ambient temperature. The properties of the aqueous mixture thus obtained are the following: - theoretical solids content: 6.6%, - solids content measured in the solution: 6.9%, - this is a honey-colored translucent product, viscous, - Viscosity ( in section 4 according to DIN EN ISO 2433 / ASTM D5125): 80 sec, - after aging at 40 ° C, the product forms a gel after only 10 days of storage (no flow, viscosity not measurable.) EXAMPLE 3 according to the invention: SEMI-FINISH SF3 Preparation of an aqueous mixture based on amic acid polyacid (PAA) and aminosilane (with a co-solvent). The PAA used has terminal groups of the order of 200 meq KOH / g.
    [0011] Aminosilane used is 3-amino propyl triethoxysilane in aqueous solution, and in particular the product marketed by Degussa under the trade name Dynasylan AMEO. The co-solvent N-ethylmorpholine or 4-acetylmorpholine, RN-CAS: 1696-20-4 The silicon content of this solution leads to a final rate on the dry film of the order of 2%. An aqueous semi-finished mixture is prepared comprising the following compounds, their respective amounts being indicated in g for: polyamide amino acid (35.5% solids): 18.15 g - N-Ethyl Morpholine: 61.08 g 3-amino propyl triethoxysilane (APTES) (100%): 1.06 g - Demineralized water: 19.71 g, 10 - Triethylamine: 0.932 g TOTAL: 100.93 g To carry out the semi-finished aqueous mixture, the following procedure is carried out: The amic acid polyamide powder is introduced into a reactor and is solubilized in the non-labeled solvent Toxic, and then, with slow stirring, 3-amino propyl triethoxysilane (APTES) is introduced into the mixture; - mechanically stirred with a pale marine for at least 2 hours with a Rayneri; A clear and homogeneous solvent solution is obtained. The stirring system is then changed, a shearing blade adapted to a rayeri is used, and distilled water is added dropwise with a dropping funnel at a rate of the order of 0.0015 g / min; a change of solvent phase is observed towards a perfectly dispersed aqueous phase; an emulsion is obtained with a milky and stable product; In order to improve the stability of the viscosity of this sol-gel emulsion, a base is added, such as trietlyamine, which makes it possible to have an ambient stability of several weeks.
    [0012] The properties of the aqueous mixture thus obtained are as follows: theoretical solids content: 6.9%, dry extract measured in the solution: 7.2%, pH = 10.4, it is a milky and stable product, Viscosity (in section 2.5 according to DIN EN ISO 2433 / ASTM D5125): 42 sec. EXAMPLE 4 according to the invention: SEMI-FINISH SF4 Preparation of an aqueous mixture based on polyamido amic acid (PAA) and aminosilane (with a co-solvent).
    [0013] The PAA used has terminal groups of the order of 200 meq KOH / g. A PAI resin, TORLON AI 3OLM from Solvay is used. Aminosilane used is 3-amino propyl triethoxysilane in aqueous solution. Reference Dynasylan AMEO 20 from DEGUSSA. The co-solvent dimethyl sulfoxide DMSO which is unlabeled The silicon content of this solution leads to a final rate on the dry film of the order of 2%. An aqueous semi-finished mixture is prepared comprising the following compounds, their respective amounts being indicated in g for: polyamide amino acid (35.5% solids): 18.15 g - DMSO: 61.08 g 30 - 3 -amino propyl triethoxysilane (APTES) (100%): 1.06 g - Demineralized water: 19.71 g, - Triethylamine: 0.932 g TOTAL: 100.93 g To prepare the aqueous semi-finished mixture, proceed as follows: in a reactor the amic acid polyamide powder which is solubilized in the unlabeled solvent; - Then, is introduced, with slow stirring, into the mixture, 3-amino propyl triethoxysilane (APTES); The mixture is stirred mechanically with a pale marine for at least 2 hours with a Rayneri; A clear and homogeneous solvent solution is obtained. the stirring system is then changed, a shearing blade adapted to a rayneri is used, then distilled water is added dropwise with a dropping funnel with a flow rate of the order of 0.0015 g / min; a change of solvent phase is observed towards a perfectly dispersed aqueous phase; An emulsion is obtained with a milky and stable product; In order to improve the stability of the viscosity of this sol-gel emulsion, a base, such as trietlyamine, is added which makes it possible to have an ambient stability of several weeks. The properties of the aqueous mixture thus obtained are as follows: theoretical solids content: 6.9%, dry extract measured in the solution: 7.2%, pH = 10.4, it is a milky and stable product, Viscosity (in section 2.5 according to DIN EN ISO 2433 / ASTM D5125): 42 sec. EXAMPLE 5 according to the invention: SEMI-FINISH SF5 Preparation of an aqueous mixture based on polyamide imide (PAI with a co-solvent) and aminosilane.
    [0014] The PAI used is a PAI resin, RHODEFTAL 210ES from HUNTSMAN whose solids content is 29% in N-ethyl pyrrolidone. Aminosilane used is 3-amino propyl triethoxysilane in aqueous solution. Reference Dynasylan AMEO from DEGUSSA. The silicon content of this solution leads to a final rate on the dry film of the order of 2%. An aqueous semi-finished mixture is prepared comprising the following compounds, their respective amounts being indicated in g for: polyamide imide (at 29% solids content): 24.05 g 15 - N-Ethyl Pyrrolidone: 53.46 g - 3- amino propyl triethoxysilane (APTES) (100%): 1.15 g - demineralized water: 21.34 g, - triethylamine: 0.932 g TOTAL: 100.93 g To carry out the semi-finished aqueous mixture, the following procedure is carried out: in a reactor, the polyamide imide which is diluted in the same solvent, N-ethylpyrrolidone. 3-amino propyl triethoxysilane (APTES) is then introduced with slow stirring into the mixture. The mixture is stirred mechanically with a pale marine for at least 2 hours with a Rayneri; A clear and homogeneous solvent solution is obtained. The stirring system is then changed, a pale shear adapted to a rayneri is used, and distilled water is added dropwise with a dropping funnel at a rate of the order of 0.0015 g / min; a change of solvent phase is observed towards a perfectly dispersed aqueous phase; An emulsion is obtained with a milky and stable product; In order to improve the stability of the viscosity of this sol-gel emulsion, a base, such as trietlyamine, is added which makes it possible to have an ambient stability of several weeks. The properties of the aqueous mixture thus obtained are the following: - theoretical solids content: 7.42%, - dry extract measured in the solution: 7.6%, - pH = 10.4 - it is a milky and stable product, - Viscosity (in section 2.5 according to DIN EN ISO 2433/15 ASTM D5125): 45 sec. EXAMPLE 6 according to the invention: SEMI-FINISH SF6 Preparation of an aqueous mixture based on polyamide auric acid (PAA) and silazane (with a co-solvent). The PAA used has terminal groups of the order of 200 meq KOH / g. As the silazane, hexamethyldisilazane of molar mass 161.39 g is used. A PAA resin, TORLON AI 3OLM from Solvay is used. The silicon content of this solution leads to a final rate on the dry film of the order of 3%. Aminosilane used is 3-amino propyl triethoxysilane in aqueous solution (in particular the product sold by DEGUSSA under the name Dynasylan AMEO). The co-solvent is N-Ethylmorpholine (or 4-acetylmorpholine), RN-CAS: 1696-20-4. The silicon content of this solution leads to a final rate on the dry film of the order of 3%.
    [0015] An aqueous semi-finished mixture is prepared comprising the following compounds, their respective amounts being indicated in g for: polyamide amino acid (at 35.5% solids): 18.15 g - N-Ethyl Morpholine: 61.08 g hexamethyldisilazane (100%): 1.06 g - demineralized water: 19.71 g, - triethylamine: 0.932 g TOTAL: 100.93 g To prepare the semi-finished aqueous mixture, the following procedure is carried out: polyamide amic acid which is solubilized in the toxic unlabeled solvent; Hexamethyldisilazane is then introduced with slow stirring into the mixture; The mixture is stirred mechanically with a pale marine for at least 2 hours with a Rayneri; a clear and homogeneous solvent solution is obtained; The stirring system is then changed, a pale shear adapted to a rayneri is used, and distilled water is added dropwise with a dropping funnel at a rate of the order of 0.0015 g / min; a change of solvent phase is observed towards a perfectly dispersed aqueous phase; An emulsion is obtained with a milky and stable product. In order to improve the stability of the viscosity of this sol-gel emulsion, a base, such as trietlyamine, is added which makes it possible to have an ambient stability of several weeks. The properties of the aqueous mixture thus obtained are as follows: theoretical solids content: 6.9%, dry extract measured in the solution: 7.2%, pH = 10.4, it is a milky and stable product, - Viscosity (in section 2.5 according to DIN EN ISO 2433 / ASTM D5125): 39 sec. EXAMPLE 7 COMPARATIVE Preparation of a fluorinated primer P1 from the semi-finished product SF1: Preparation of a fluorinated primer The level of silicon provided by the APTES of this solution gives a final rate on the dry film of the order of 0.5%. A fluorinated aqueous mixture of primer is prepared from the semifinished SF1 comprising the following compounds, their respective quantities being indicated in g for: - Colloidal dispersion of PTFE (at 60% solids content): 289.28 g - Carbon black (at 25% solids content in water): 40.82 g - Colloidal silica (at 30% solids content in water): 164.58 g - semi-finished SF1 (at 6% solids content in water): 236.99g - Surfactant system (at 12% solids in water): 51.35g - Demineralized water: 216.97g, - 3-amino propyl triethoxysilane (APTES) (100%) %): 9.4g - Triethylamine: 2.0 g - Demineralised water: 204.8 g, TOTAL: 1216.2 g The properties of the aqueous mixture thus obtained are the following: - theoretical solids content: 22.2%, - solids content measured in the solution: 22.9%, - pH = 8.5 - Viscosity (in section 2.5 according to DIN EN ISO 2433 / ASTM D5125): 65 sec - this is a milky but very unstable product which settles irreversibly. The addition of APTES in post-addition in a fluorinated primer leads to rapid condensation of the silanol groups with the formation of an irreversible gel. This primary is not applicable. EXAMPLE 8 ACCORDING TO THE INVENTION Preparation of a Fluorinated Primer P2 from the SF3 Semi-Finish A fluorinated aqueous mixture of primer is prepared from the SF3 semi-finished product comprising the following compounds, their respective amounts being indicated in g for: 20 - Colloidal dispersion of PTFE (at 60% solids content): 298.32 g - Carbon black (at 25% solids content in water): 42.09 g - Colloidal silica 25 (at 30% solids content) in water): 169.72 g - semi-finished SF3 (at 6.9% dry extract in water + N-ethylmorpholine): 213.17g - System of surfactants - (at 12% of extract dry in water): 52.95 g 30 - Demineralized water: 223.74 g, TOTAL: 1000.0 g The properties of the aqueous mixture thus obtained are as follows: theoretical solids content: 26.2%, dry extract measured in the solution: 25.9 %, pH = 8.5 Viscosity (in section 2.5 according to DIN EN ISO 2433 / ASTM D5125): 50 sec, this is a milky product that is very stable, no change in viscosity at ambient temperature of more than 5% over 2 months of storage.
    权利要求:
    Claims (13)
    [0001]
    REVENDICATIONS1. An aqueous composition comprising a polyimide, a polyamide imide or polyamide-amic acid, a Lewis base, a polar aprotic solvent, with at least 15% water relative to the total weight of said composition, characterized in that the Lewis base is an aminosilane or a silazane.
    [0002]
    2. A composition according to claim 1, wherein the aminosilane or silazane is present in said composition in an amount of 0.1 to 10% by weight of said composition.
    [0003]
    3. The composition of claim 1 or 2, wherein the aminosilane is 3-amino propyltriethoxysilane (APTES).
    [0004]
    The composition of claim 1 or 2, wherein silazane is hexamethyldisilazane. 20
    [0005]
    5. Composition according to any one of the preceding claims, wherein the polar aprotic solvent is present in a proportion of 1 to 70% by weight relative to the total weight of the composition. 25
    [0006]
    6. Composition according to preceding claims, in polar is N-ethyl morpholine. 30
    [0007]
    7. A primer composition comprising any aqueous composition of the fluorocarbon claims 1. non-stick coating any of which the aprotic solvent as defined in one to 6 and a dispersion of
    [0008]
    The composition of claim 7, wherein the fluorocarbon resin is selected from the group consisting of polytetrafluoroethylenes (PTFE), the tetrafluoroethylene and perfluoropropylvinylether (PFA) copolymers, the tetrafluoroethylene and hexafluoropropene (FEP) copolymers, the polyfluoromethylenes. vinylidene (PVDF), MVA (TFE / PMVE copolymer), TFE / PMVE / FAVE terpolymers, ETFE, and mixtures thereof.
    [0009]
    9. Composition according to claim 8, wherein the fluorocarbon resin is polytetrafluoroethylene (PTFE), or a mixture (PTFE / PFA) of polytetrafluoroethylene (PTFE) and copolymer of tetrafluoroethylene and perfluoropropylvinylether (PFA), or a mixture (PTFE) / FEP) of polytetrafluoroethylene (PTFE) and copolymer of tetrafluoroethylene and hexafluoropropene (FEP).
    [0010]
    10. A process for preparing a release coating primer composition comprising the following steps: - a polyimide polymer, or polyamide imide or polyamide-amic acid is dissolved in a polar aprotic solvent to form a homogeneous mixture; a Lewis base is introduced into said mixture to fix it on said polymer; water is added to the mixture thus formed; and optionally, a second Lewis base, which is neither a silane nor a silazane, is added to said mixture. The fluorocarbon dispersion is added. Optionally, charges and / or pigments are additionally added to said mixture.
    [0011]
    11. A method of manufacturing an article comprising the following steps: - providing a metal substrate having two opposite faces; the application on one of the faces of said substrate of at least one layer of primer composition as defined in any one of claims 7 to 9; the application on said layer of primer composition of at least one topcoat layer comprising at least one fluorocarbon resin; then - cooking the assembly at a temperature between 370 ° C and 430 ° C.
    [0012]
    12. Article obtainable by the process as defined in claim 11.
    [0013]
    13. Article according to claim 12, constituting a culinary article one of whose faces constitutes an inner face intended to be in contact with food placed inside said article and the other side is a convex outer face intended to be in contact with a heat source.15
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    KR102204023B1|2021-01-18|
    WO2015092262A1|2015-06-25|
    EP3082527B1|2020-11-04|
    KR20160102462A|2016-08-30|
    JP2017511389A|2017-04-20|
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    法律状态:
    2015-12-31| PLFP| Fee payment|Year of fee payment: 3 |
    2016-12-29| PLFP| Fee payment|Year of fee payment: 4 |
    2017-06-23| CA| Change of address|Effective date: 20170518 |
    2018-01-02| PLFP| Fee payment|Year of fee payment: 5 |
    2018-12-31| PLFP| Fee payment|Year of fee payment: 6 |
    2019-12-30| PLFP| Fee payment|Year of fee payment: 7 |
    2020-12-28| PLFP| Fee payment|Year of fee payment: 8 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1363355A|FR3015507B1|2013-12-20|2013-12-20|AQUEOUS COMPOSITIONS FOR PRIMERS OF ANTI-ADHESIVE COATINGS AND PROCESS FOR THEIR PREPARATION|FR1363355A| FR3015507B1|2013-12-20|2013-12-20|AQUEOUS COMPOSITIONS FOR PRIMERS OF ANTI-ADHESIVE COATINGS AND PROCESS FOR THEIR PREPARATION|
    JP2016541585A| JP6700184B2|2013-12-20|2014-12-16|Aqueous compositions for non-adhesive coatings and methods for their preparation|
    PCT/FR2014/053368| WO2015092262A1|2013-12-20|2014-12-16|Aqueous compositions for primary anti-adhesive coating and preparation method thereof|
    EP14828219.7A| EP3082527B1|2013-12-20|2014-12-16|Aqueous compositions for primary anti-adhesive coating and preparation method thereof|
    KR1020167019135A| KR102204023B1|2013-12-20|2014-12-16|Aqueous compositions for primary anti-adhesive coating and preparation method thereof|
    US15/105,433| US20170002209A1|2013-12-20|2014-12-16|Aqueous Compositions for Primary Anti-Adhesive Coating and Preparation Method Thereof|
    CN201480069681.5A| CN105828676B|2013-12-20|2014-12-16|Aquo-composition and preparation method thereof for non-sticking lining priming paint|
    US16/852,992| US20200248001A1|2013-12-20|2020-04-20|Aqueous Compositions for Primary Anti-Adhesive Coating and Preparation Method Thereof|
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