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    • 专利摘要:
    The present invention relates to an aqueous composition for amine-free coating comprising at least one heterocyclic polymer, characterized in that the heterocyclic polymer is in the form of a powder having a d90 of less than or equal to 20 μm. The subject of the present invention is also an aqueous amine-free release coating composition comprising such an aqueous coating composition, as well as their respective methods of manufacture. The present invention further relates to a method of manufacturing an article on one side of a metal substrate, at least one coating composition layer or a non-stick coating composition layer according to the present invention. invention.
    公开号:FR3022552A1
    申请号:FR1463460
    申请日:2014-12-30
    公开日:2015-12-25
    发明作者:Barbara Gantillon；Laurent Voisin；Isabelle Joutang；Jean-Luc Perillon
    申请人:SEB SA；
    IPC主号:
    专利说明:

    [0001] This invention relates generally to aqueous coating compositions (or semi-finished or semi-finished compositions) as well as aqueous non-stick coating compositions (1). The present invention relates generally to aqueous coating compositions (or semifinished or semi-finished compositions) as well as aqueous non-stick coating compositions ( or primary or primary compositions) comprising such coating compositions. The release coatings obtained from the coating compositions and release coating compositions of the present invention exhibit improved corrosion and abrasion resistance, as well as reduced yellowing. For the purposes of the present invention, the term "aqueous composition" is intended to mean any composition comprising in the majority water, that is to say at least 50% water by weight relative to the total weight of said composition. The invention belongs to the field of the formulation of semi-finished and non-stick coating primers intended to be applied to heating articles, and more particularly to cooking or household appliances, as well as to the field of such non-stick coatings.
    [0002] Examples of culinary articles that can be used in the context of the present invention include stoves, saute pans, saucepans, woks, crepe makers, casseroles, pots, casseroles, roasters. with eggs and grill stoves. As examples of household electrical appliances used in the context of the present invention, there may be mentioned deep fryer vats, pans or fondue pots fondue or raclette, and iron soleplates. It is particularly known to those skilled in the art that culinary articles must meet performance criteria as to their anti-adhesiveness, their scratch resistance and, more generally, their resistance to multiple attacks to which they are subjected in use. Fluoropolymer-based coatings offer the best compromise for all of these properties. However, there remains a difficulty for the adhesion of these coatings on the support of the article and many solutions have been proposed. An important part of the formulations intended to promote the adhesion of polytetrafluoroethylene (PTFE) is carried out using a co-resin of adhesion. Among the most used resins, there are heterocyclic polymers, such as polyamide-imides (PAI) and polyimides (PI). For use in combination with the colloidal dispersions of PTFE, these co-resins of adhesion must necessarily be previously put in aqueous phase generally in two modes.
    [0003] By heterocyclic polymer is meant, in the sense of the present invention, any polymer having at least one monomeric unit comprising at least one heterocycle. For the purposes of the present invention, heterocycle means any ring having at least two different elements as ring member atoms.
    [0004] For the first mode, the starting material is a heterocyclic polymer resin dissolved in a polar aprotic solvent, such as N-ethylpyrrolidone (NEP) or N-methylpyrrolidone (NMP). Then, salification of the acidic groups is carried out by adding very basic primary or secondary amines, and then water is introduced into the mixture in order to phase invert the mixture. It should be noted that most polar aprotic solvents are subject to labeling as a harmful or even toxic product in the REACH regulation (Regulation of the European Parliament and of the Council on the registration, evaluation and authorization of chemical substances, as well as the restrictions applicable to these substances). As a result, the impact on the environment and the health generated by such use is not negligible. For the purpose of the present invention, the term "toxic or harmful solvent" means a solvent containing carcinogenic, mutagenic or reprotoxic substances of category 1A and 1B and on which danger pictograms must be affixed to inform users of the risks and dangers. associated with this type of product (as defined by Regulation EC 3022552 3 N ° 1272/2008 of the European Parliament and the Council of 16 September 2008 and its adaptations to scientific and technical progress). For the second mode, the starting material is a hydro-emulsifiable powder heterocyclic polymer resin, to which one or more amines are added to salify the acidic groups of the heterocyclic polymer and create an emulsion in hot water. From a functional point of view, the first mode using heterocyclic polymer resins in solution in a polar aprotic solvent is easier to implement.
    [0005] However, the use of salification amines results in the opening of the imide rings of the heterocyclic polymer and, as a result, the filming is often poorer than expected and the adhesion and / or corrosion resistance of the coating obtained are weakened. Finally, the use of salification amines, whatever their type, accentuates the yellowing during the preparation of the coating. To overcome the disadvantages of the prior art, the Applicant has developed aqueous semi-finished and primer compositions for obtaining coatings resistant to high temperatures and abrasion, and having a reduced surface yellowing, nonexistent.
    [0006] More particularly, the subject of the present invention is an aqueous amine-free coating composition (or semi-finished composition), and comprising at least one heterocyclic polymer, the heterocyclic polymer (s) being in the form of a powder having a d90 less than or equal to 20 pm.
    [0007] Such a particle size makes it possible to obtain coatings of small thicknesses resistant to abrasion. In addition, this particle size makes it possible to attenuate the sedimentation effect in the semi-finished composition. For the purposes of the present invention, the term "d90" means the dimension such that 90% by volume of the population consists of particles of size less than said dimension. Advantageously, the heterocyclic polymer or polymers are in the form of a powder that also has a d50 of less than or equal to 10 μm. For the purposes of the present invention, the term "d50" means the dimension such that 50% by volume of the population consists of particles of size less than said dimension (median of the particle distribution). Advantageously, the heterocyclic polymer or polymers are in the form of a powder having a minimum d50 of the order of 3 μm and a minimum d90 of 10 μm. According to the present invention, the semi-finished composition is free of amines. For the purposes of the present invention, the term "amine" means any nitrogen compound which is formally derived from NH 3 ammonia by replacing one or more hydrogen atoms with carbon groups, such as primary amines and secondary amines. tertiary amines, heterocyclic amines, aliphatic diamines, aliphatic oligoamines, etheramines, ethanolamines, isopropanolamines and alkyls aminoalcohol.
    [0008] Advantageously, the semi-finished composition according to the invention comprises at most 15% by weight of solvent relative to the total weight of the semi-finished composition. The solvent used in the semifinished composition according to the present invention can advantageously be polar aprotic. The solvent may preferably comprise at least one of N-formylmorpholine (NFM), dimethylsulfoxide (DMSO), N-acetylmorpholine (NAM), N-ethylpyrrolidone (NEP) and N-methylpyrrolidone. (NMP). In order to obtain unlabeled (i.e. non-toxic) primer compositions, it is necessary that the concentration of the toxic polar aprotic solvent, so-called labeled, be as low as possible, or even as it is null. A source of this type of solvent comes from a residual content present in the heterocyclic polymer powder. In addition, incorporating only a small amount of such a solvent in the semifinished composition limits the yellowing of the coating. In addition to yellowing, a high content of these toxic polar aprotic solvents is unnecessarily expensive. Therefore, the semifinable composition according to the invention preferably comprises at most 2% by weight, and preferably at most 0.3% by weight, of polar aprotic solvent toxic to the total weight of the semi-finished composition. Advantageously, the polar aprotic solvent is nontoxic. The heterocyclic polymer (s) may advantageously each have an acid number of from 1 to 200 mg KOH / g. Advantageously, this or these heterocyclic polymers are selected from the group comprising polyimides (PI), polyamide-imides (PAI), polyetherimides (PEI), polyamide-amic acids and mixtures thereof. These polymers have a high thermal resistance and a good hardness that can be associated with the aromatic units of their structure. For example, the semi-finished composition according to the invention may comprise a mixture of polyamide-imide and polyamide-amic acid. Advantageously, the degree of polymerization of the aforementioned heterocyclic polymer (s) is greater than or equal to 5. By polymerization degree of a polymer is meant, in the sense of the present invention, the number of repetitions of the basic unit or units in this polymer. According to one embodiment of the present invention, the coating composition as described above may further comprise at least one aromatic polymer whose acid number is strictly less than 1 mg KOH / g, and preferably equal to 0 mg of KOH / g, and which is in the form of a powder having a d90 of less than or equal to 20 μm, the relative content by weight of the heterocyclic polymer relative to the aromatic polymer in the coating composition being greater than 50: 50 and less than 100: 0.
    [0009] Advantageously, the combination of such an aromatic polymer with the heterocyclic polymer described above makes it possible to further limit the yellowing of the coatings obtained. For the purposes of the present invention, the term "aromatic polymer" means any polymer having at least one monomeric unit comprising at least one ring system that complies with Hückel's aromaticity rule. Advantageously, this or these aromatic polymers are selected from the group comprising polyethersulfones (PES), polyether ether sulfones (PEES), polyphenylsulfones (PPSU), polyphenylene sulphide (PPS), polyetheretherketones (PEEK), polyetherketones ( PEK), polyetherketonecetones (PEKK), polyetheretherketoneketones (PEEKK), polyetherketoneetherketoneketones (PEKEKK), and derivatives and mixtures thereof.
    [0010] Advantageously, the degree of polymerization of the abovementioned aromatic polymer (s) is greater than or equal to 5. The subject of the present invention is also an aqueous nonstick coating composition (or aqueous primer composition) free of amine, which comprises: an aqueous composition for coating as defined above, and - at least one fluorocarbon resin. Preferably, the primer composition according to the invention comprises between 2% to 20% by weight, and preferably 8% to 15% by weight, of solvent relative to the total weight of said aqueous primer composition. Advantageously, the solvent used in the aqueous primer composition is polar aprotic. The solvent may preferably comprise at least one of N-formylmorpholine (NFM), dimethylsulfoxide (DMSO), N-acetylmorpholine (NAM), N-ethylpyrrolidone (NEP) and N-methylpyrrolidone. (NMP). The primer composition according to the invention advantageously comprises at most 1% by weight, and preferably at most 0.3% by weight, of toxic polar aprotic solvent relative to the total weight of the aqueous primer composition.
    [0011] Advantageously, the polar aprotic solvent is nontoxic. The polar aprotic solvent may preferably comprise at least one of N-formylmorpholine (NFM), dimethylsulfoxide (DMSO). Incorporating a non-toxic polar aprotic solvent into the composition provides an unlabeled (in other words nontoxic) primer composition.
    [0012] 30 Thus, the risks and dangers related to the environment and to the health of others are limited. In addition, the use of non-toxic formulations is greatly facilitated because these formulations can be implemented with only a minimum of precautions.
    [0013] Advantageously, the fluorocarbon resins are selected from the group comprising polytetrafluoroethylene (PTFE), copolymers of tetrafluoroethylene and perfluoropropylvinyl ether (PFA), copolymers of tetrafluoroethylene and hexafluoropropene (FEP), polyvinylidene fluoride (PVDF), copolymers of tetrafluoroethylene and polymethylvinyl ether (MVA), terpolymers of tetrafluoroethylene, polymethylvinylether and fluoroalkylvinylether (TFE / PMVE / FAVE), ethylene tetrafluoroethylene (ETFE), and mixtures thereof. Advantageously, the fluorocarbon resin is polytetrafluoroethylene (PTFE), or a mixture of PTFE and PFA (PTFE / PFA), or a mixture of PTFE and FEP (PTFE / FEP). Advantageously, the fluorocarbon resin represents 1 to 99% by weight, and preferably 30 to 80% by weight, of the total dry weight of the primer composition.
    [0014] In the case where the primer composition does not comprise an aromatic polymer as mentioned above, the relative content by weight of the heterocyclic polymer with respect to the fluorocarbon resin is between 20:80 and 25:75. In the case where the primer composition comprises at least one aromatic polymer as mentioned above, the relative total content by weight of the heterocyclic polymer and the aromatic polymer with respect to the fluorocarbon resin is between 20:80 and 25:75. Advantageously, the primer composition according to the invention further comprises at least one filler.
    [0015] Advantageously, the filler is less than 40% by weight, and preferably 3 to 20% by weight, of the total dry weight of the primer composition. Advantageously, the filler comprises silica nanoparticles and / or alumina nanoparticles and / or silicon carbide nanoparticles. The present invention also relates to a process for preparing an aqueous coating composition as defined above comprising the following steps: a) providing at least one heterocyclic polymer in powder form; b) preparing a mixture comprising water and the powder of step a), and c) grinding the mixture resulting from step b) to obtain a ground mixture comprising the heterocyclic polymer in the form of powder having a d90 less than or equal to 20 μm. Advantageously, in this process for preparing a semifinished composition according to the invention, solvent is added: during the preparation of step b), and / or to the ground mixture resulting from the step c), the total content of solvent in the coating composition being at most 15% by weight relative to the total weight of said coating composition.
    [0016] According to one embodiment of the process for preparing a semi-finished composition according to the invention, the process further comprises a step a) of supplying at least one aromatic polymer whose acid number is equal to 0 mg of KOH / g and which is in the form of a powder, and in which: the mixture resulting from stage b) additionally comprises the powder of stage a '), and - grinding of step c) makes it possible to obtain a ground mixture comprising the heterocyclic polymer and the said powdery aromatic polymer having a d90 of less than or equal to 20 μm, and the relative weight content of the heterocyclic polymer relative to the aromatic polymer. in the ground mixture from step c) is greater than 50:50 and less than 100: 0. Advantageously, in the process for preparing a semi-finished composition according to this embodiment, solvent is added: during the preparation of step b), and / or to the ground mixture derived from the step c) the total solvent content in the semifinished composition being at most 15% by weight relative to the total weight of said semifinished composition.
    [0017] According to another embodiment of the process for preparing a semi-finished composition according to the invention, the process also comprises the following steps: a ') the supply of at least one aromatic polymer whose index 5 is 0 mg KOH / g and is in the form of a powder, b ') the preparation of a mixture comprising water and the powder of step a'), c ') grinding the mixture resulting from step b ') to obtain a ground mixture comprising said powdery aromatic polymer having a d90 of less than or equal to 20 μm, and d) the mixture of the ground mixture resulting from stage c ) and the ground mixture from step c '), the relative weight content of the heterocyclic polymer with respect to the aromatic polymer in the mixture resulting from step d) being greater than 50:50 and less than 100: 0 . Advantageously, in the process for preparing a semi-finished composition according to this other embodiment, solvent is added: - during the preparation of step b), and / or - during the preparation of the step b '), if appropriate, and / or - to the ground mixture resulting from stage c), and / or - to the ground mixture resulting from stage c'), if appropriate, and / or - to mixture resulting from step d), if appropriate, the total content of solvent in the semifinished composition being at most 15% by weight relative to the total weight of said semifinished composition.
    [0018] The present invention also relates to a method for preparing an aqueous coating composition comprising at least one aromatic polymer as defined above comprising the following steps: a) providing at least one heterocyclic polymer in the form of powder a ') providing at least one aromatic polymer whose acid number is 0 mg KOH / g and which is in powder form, b) the preparation a mixture comprising water and the powder of step a), e) grinding the mixture resulting from step b) to obtain a ground mixture comprising the heterocyclic polymer, f) the preparation of a mixture comprising the ground mixture resulting from stage e) and the powder of stage a '), and g) grinding the mixture resulting from stage f) to obtain a ground mixture comprising the heterocyclic polymer and said aromatic polymer in powder form having a lower d90 or equal 1 to 20 pm, the relative content by weight of the heterocyclic polymer with respect to the aromatic polymer in the mixture resulting from step g) being greater than 50:50 and less than 100: 0. Advantageously, in this process for preparing a semi-finished composition comprising at least one aromatic polymer, solvent is added: during the preparation of step b), and / or to the ground mixture obtained from the step e), and / or - during the preparation of step f), and / or - to the ground mixture resulting from step g), if appropriate, the total content of the solvent in the sem composition -fini being at most 15% by weight relative to the total weight of said semifinished composition. Another subject of the present invention is another process for preparing an aqueous coating composition comprising at least one aromatic polymer as defined above, comprising the following steps: a) providing at least one heterocyclic polymer in the form of a powder a ') providing at least one aromatic polymer having an acid number of 0 mg KOH / g and which is in the form of a powder, b') preparing a mixture comprising the water and the powder of step a '), e') grinding the mixture from step b ') to obtain a ground mixture comprising the aromatic polymer, 3022552 11 f') the preparation of a mixture comprising the ground mixture resulting from stage e ') and the powder of stage a), and g') milling the mixture resulting from stage f ') to obtain a ground mixture comprising the heterocyclic polymer and the polymer aromatic powder form having a d90 less than or equal to at 20 pm, the relative content by weight of the heterocyclic polymer with respect to the aromatic polymer in the mixture resulting from step g ') being greater than 50:50 and less than 100: 0. Advantageously, in this process for preparing a semi-finished composition comprising at least one aromatic polymer, solvent is added: during the preparation of step b ') and / or to the ground mixture obtained from step e '), and / or - during the preparation of step f'), and / or - to the ground mixture resulting from step g '), where appropriate, the total content of solvent in the semifinished composition being at most 15% by weight based on the total weight of said semifinished composition. Advantageously, the grinding in any one of the processes for preparing a semifinished composition according to the invention is mechanical grinding at room temperature or ultrasonic grinding. The present invention also relates to a process for the preparation of an aqueous release coating composition as defined above comprising mixing the aqueous coating composition as defined above or as prepared according to any of the preparation methods. a coating composition as defined above with at least one fluorocarbon resin. The fluorocarbon resins may be in powder form or in aqueous dispersion. The present invention also relates to a method of manufacturing an article comprising the following steps: i. providing a metal substrate having two opposite faces; 3022552 12 ii. the application, on one of the faces of said substrate, of at least one layer of aqueous semi-finished composition as defined above or as prepared according to any one of the processes for preparing a coating composition such as defined above or at least one layer of aqueous primer composition as defined above or as prepared according to the process for preparing a non-stick coating composition as defined above; then iii. baking the assembly at a temperature between 300 ° C and 430 ° C.
    [0019] Advantageously, the method of manufacturing an article according to the invention may further comprise, between the steps of application ii) and cooking iii), the application, on said layer of semi-finished composition or of primer composition of at least one topcoat layer comprising at least one fluorocarbon resin.
    [0020] The present invention further relates to an article capable of being obtained according to the method of manufacturing an article as described above. The article according to the invention may be a culinary article one of whose faces constitutes a concave inner face intended to be in contact with food placed inside said article and the other side is a convex outer face intended to to be in contact with a source of heat. The invention is illustrated in more detail in the following examples.
    [0021] EXAMPLES Products Supports 30 - Smoothed aluminum supports simply degreased Aqueous semi-finished compositions - Triethylamine 30 2 2 5 5 13 13 - Heterocyclic polymer resins: o polyamide-amic acid in the form of a 35.5% aqueous wet powder dry extract (ES) and containing less than 5% by weight of N-methylpyrrolidone (NMP), having a food grade and the degree of polymerization is of the order of 8 o polyamide-amic acid in the form of a wet powder 90% aqueous dry matter (ES) and containing less than 5% by weight of N-methylpyrrolidone (NMP), having a food grade and whose degree of polymerization is of the order of 10 to 20% polyamide resin -imide (PAI) 29% dry extract in N-ethylpyrrolidone (NEP), the degree of polymerization is of the order of 10 to 15 - Other polymer resins: o polyethersulfone resin (PES), micronized grade, whose degree of polymerization is greater than 50 - aprotic solvents Non-labeled (ie nontoxic for the purposes of the present invention) polar ions: N-formylmorpholine (NFM) - labeled polar aprotic solvents (ie, toxic for the purpose of the present invention) N-ethylpyrrolidone (NEP) Aqueous primer compositions - Non-labeled polar aprotic solvents (ie non-toxic for the purpose of the present invention): o N-formylmorpholine (NFM) o dimethyl sulfoxide (DMSO) - Polar labeled aprotic solvents (ie, toxic for the purpose of the present invention): n-Ethylpyrrolidone (NEP) - Charge: surface unmodified colloidal silica with a specific surface area of about 220 m2 / g and which is in the form of an aqueous dispersion of nanoparticles with a solids content of 30% by weight. 13% to 13% - Dispersion of carbon black at 25% solids content - Dispersion of PTFE at 60% solids content - Surfactant system nonionic alkylphenol ethoxylated dry extract 5 - Ammonium hydroxide NH4OH (d = 0.9) Tests Determination of the solids content of an aqueous semi-finished or primer composition PRINCIPLE The solids content of a product is the residual solid portion remaining after evaporation. volatile matter it contains. The temperature and the drying time play an important role because the high boiling solvents, the monomer fractions, the reactive diluents and the reaction by-products (depending on their degree of retention) leave the film in formation very slowly. . It is therefore very important to define, in a very conventional manner, standardized drying conditions as close as possible to the practice. PROCEDURE To measure this dry extract, the procedure is as follows: an aluminum cup is weighed: mo = mass of the cup; there is between 0.5 g and 3 g of product to be studied in this cup; the loaded cup is weighed: m1 = mass of the filled cup; the cup is placed in an oven at 210 ° C. for two hours; - After steaming and after cooling, the cup is weighed: 30 m2 = mass of the cup filled after steaming and cooling; the dry extract is given by the formula below: Dry extract = 1001 (m2-mo) / (half-mo) 3022552 Measuring the size and particle size distribution by diffraction of light for powders of size between about 100 nm and about 5 mm At the end of grinding of the products of the present invention, the milled powder is recovered and its particle size characterized using a laser diffraction granulometer marketed under the name Commercial Mastersizer from the company Malvern. Evaluation of adhesion of a semifinished or primer layer to a smooth aluminum substrate A grid test according to ISO 2409 followed by immersion of the coated article for 18 hours (consisting of alternately 3 cycles of 3 hours in boiling water and 3 cycles of 3 hours in oil at 200 ° C). Then, it is observed whether the non-stick coating has a peel or not. The quotation is as follows: - no square must be taken off to obtain a quotation of 100 (excellent adhesion); - in case of detachment, the value recorded is equal to the quotation of 100 20 less the number of squares taken off. Evaluation of yellowing The yellowing after baking of the coated wafers is evaluated visually by inter-wafer comparison.
    [0022] Operating Principle of the Jar Mill (Mechanical Grinding) PRINCIPLE Ball milling involves loading a jar with the sample to be milled and so-called grinding beads and rotating the jar about its axis at a certain speed. The rotation of the jar is usually done using a roller machine. The sample may be milled in dry form or dispersed in a suitable solvent (eg in water, in alcohol or in a solvent). The dispersion may also contain some adjuvants (such as a dispersant or antifoam). DEFINING THE MAIN GRINDING PARAMETERS 5 - Choosing the grinding balls (volume and diameter (s)) The average diameter of the grinding balls must be adapted to the size of the particles to be grinded. The finer the particles, the smaller the diameter of the beads to be used. The total volume of beads, including voids between the beads, will represent about 50-60% of the interior volume of the jar. The beads of different sizes are advantageously distributed according to the following weight proportion relative to the total weight of the beads: 25% of small beads, 50% of medium beads and 25% of large beads. The size of the smallest balls is between 2 and 10 mm. Alumina and stabilized zirconia are commonly used as the material of the beads. - Volume of material in the mill In order to limit the wear of the grinding balls, the load to be milled must completely cover the bead load. In general, it will represent a volume corresponding to about 25% of the volume of the jar. If the load to be milled is a dry powder, the volume of the balls will be adjusted after a few minutes of grinding. As grinding reduces the particle size as well as the volume of the voids between particles, it is necessary to periodically check whether the volume of charge to be ground is sufficient to cover all the balls. If this is no longer the case, it is necessary to remove the excess beads to minimize the contamination of the powder. The duration of the grinding depends on the nature of the polymer resin to be ground and the desired final particle size.
    [0023] Functional principle of the Discontimill® mill This grinding is a mechanical grinding process which involves reducing the size of the particles and grains of different types of materials during which the suspension of the particles and grains is maintained under cooling.
    [0024] The grinding operations are carried out with a planetary mill. It consists of a disc on which are fixed two grinding jars with a capacity of 45mL each and can accommodate up to 7 grinding balls of 15 mm diameter. The jars and the grinding balls are made of zirconium oxide, a material known for its very high resistance to shocks and wear allowing grindings of prolonged duration. The grinding system works by rotating the carrier disc and the jars around their own axis. The rotation speed is identical for the tray and the jars, ranging from 100 rpm to 800 rpm. On the other hand, the 10 directions of rotation are opposed so as to generate antagonistic centrifugal forces. EXAMPLE 1 An aqueous semi-finished composition according to the invention (SF1): Preparation of an aqueous heterocyclic polymer-free SF1 semi-finished composition and without amine. An aqueous SF1 semi-finished composition is prepared comprising the following compounds, their respective amounts being indicated below: Polyamide-amic acid (35.5% ES): 616.0 g - Demineralized water: 726.3 g TOTAL: 1342.3 g To make the aqueous SF1 semi-finished composition, a 3-liter jar crushing system is used to obtain a paste consisting of a stable suspension of polyamide-amic acid particles in water of which the final particle size is important for spray coating and obtaining adhesion properties of the resulting coating. The procedure is as follows: the polyamide-amic acid powder is introduced into the jar, the initial particle size of which varies from a few hundred microns to one millimeter; then add demineralised water; the jar is placed at room temperature with the mixture thus obtained and the beads on rollers for the time necessary and sufficient to reduce the size of the polyamide-amic acid particles.
    [0025] The proportion of polar aprotic solvent toxic in the SF1 composition, namely NMP, is less than 2.3% by weight relative to the total weight of the composition. The properties of the aqueous composition SF1 thus obtained are as follows: theoretical solids content: 16.3% dry extract measured in the composition: 16.2% This is a cream-white suspension. The pH of this composition is between 3 and 4.
    [0026] Viscosity (in section 2.5 according to DIN EN ISO 2433): 45 s; the SF1 composition is still stable after 60 days of storage, and the change over time in the viscosity is less than 20%. The determination of the size of the particles by diffraction of the light using the Mastersizer laser granulometer shows that a principal peak at d50 centered on a mean diameter of between 5 and 6 μm and a d90 of 19 μm is obtained. , which confirms the suspension of all the powder. EXAMPLE 2: Semi-finished aqueous composition according to the invention (SF2): Preparation of an aqueous heterocyclic polymer-based semi-finite SF 2 composition, without amine, and with non-labeled polar aprotic solvent. An aqueous SF2 semi-finished composition is prepared comprising the following compounds, their respective amounts being indicated below: Polyamide-amic acid (35.5% ES): 616.0 g N-formylmorpholine: 130.0 g Water demineralized: 596.3 g TOTAL: 1342.3 g To produce the aqueous semifinable composition SF2, the procedure is the same as in Example 1. The proportion of polar aprotic solvent toxic in the SF2 composition, either the NMP is less than 2.3% by weight relative to the total weight of the composition.
    [0027] The properties of the aqueous composition SF2 thus obtained are as follows: theoretical solids content: 16.3%, dry extract measured in the composition: 16.2%; a suspension of creamy white color. - The pH of this composition is between 3 and 4. - Viscosity (in section 2.5 according to DIN EN ISO 2433): 50 s; the SF2 composition is still stable after 60 days of storage, and the evolution of the viscosity over time is less than 20%, 10 - The determination of the particle size by diffraction of the light using the Mastersizer laser granulometer shows that we obtain a principal peak in d50 centered on a mean diameter of between 5 and 6 pm and a d90 of 19 pm, which confirms the suspension of all the powder.
    [0028] EXAMPLE 3: An aqueous semi-finished composition according to the invention (SF3): Preparation of an aqueous semi-finished composition according to the invention based on heterocyclic polymer, without amine, and with labeled polar aprotic solvent.
    [0029] An aqueous SF3 semi-finished composition was made comprising the following compounds, their respective amounts being indicated below: Polyamide-amic acid (35.5% ES): 616.0 g N-ethylpyrrolidone: 142.0 g Water demineralized: 584.0 g - TOTAL: 1342.0 g To produce the aqueous semi-finished composition SF3, the procedure is the same as in Example 1. The properties of the aqueous composition SF3 thus obtained are as follows: : - theoretical solids content: 16.3% - dry extract measured in the composition: 16.2% - This is a cream-white suspension. The pH of this composition is between 3 and 4. Viscosity (in section 2.5 according to DIN EN ISO 2433): 50 s; the SF3 composition is still stable after 60 days of storage, and the evolution of the viscosity over time is less than 20%, - The determination of the particle size by diffraction of the light using the Mastersizer laser granulometer shows that we obtain a principal peak in d50 centered on a mean diameter of 5 to 6 pm and a d90 of 19 pm, which confirms the suspension of all the powder. EXAMPLE 4: Semifinished aqueous composition according to the invention (SF4): Preparation of an aqueous heterocyclic polymer-based SF4 semi-finished composition, without amine, and with non-labeled polar aprotic solvent. An aqueous SF4 semi-finished composition is prepared comprising the following compounds, their respective amounts being indicated below: Polyamide-amic acid (90% ES): 131.3 g N-formylmorpholine: 68.0 g Demineralized water 485.0 g TOTAL 684.3 g To make the aqueous semi-finished composition SF4, the procedure is the same as in Example 1. The proportion of polar aprotic solvent toxic in the SF4 composition, namely NMP is less than 1% by weight based on the total weight of the composition. The properties of the aqueous composition SF4 thus obtained are as follows: theoretical solids content: 17.3% solids content measured in the composition: 18.0% This is a cream-white suspension. The pH of this composition is between 3 and 4. Viscosity (in section 2.5 according to DIN EN ISO 2433): 59 s; the SF4 composition is still stable after 60 days of storage, and the evolution of the viscosity over time is less than 20%, - The determination of the particle size by diffraction of the light at using the Mastersizer laser granulometer shows that we obtain a principal peak in d50 centered on a mean diameter of between 5 and 6 pm and a d90 of 19 pm, which confirms the suspension of all the powder.
    [0030] COMPARATIVE EXAMPLE 1: Semifinished aqueous composition (SFC1): Preparation of an aqueous composition of heterocyclic polymer-based SFC1 semi-finished with an amine and labeled polar aprotic solvent.
    [0031] An aqueous semifinished SFC1 composition is prepared comprising the following compounds, their respective amounts being indicated below: PAI resin at 29% solids content in CIP: 327.9 g N-ethylpyrrolidone: 117.7 g - Triethylamine: 32.8 g Demineralized water: 521.6 g TOTAL: 1000.0 g The dissolution of the PAI comprises a step of passing through the aqueous phase by obtaining a polyamide-amic acid salt. This step is carried out in a Discontimill® brand ball mill at room temperature in the presence of amine. In the SFC1 composition, the water / amine weight ratio is about 94/6. The weight percentage of amine in the SFC1 composition is 3.3%. The weight ratio polyamide-imide / amine is about 74/26. The proportion of polar aprotic solvent in the SFC1 composition is 35.0% by weight relative to the total weight of the SFC1 composition. The properties of the aqueous composition SFC1 thus obtained are the following: - theoretical solids content: 9.5% - solids content measured in the composition: 9.3% - This is a translucent yellow solution and very viscous. 15 - Viscosity (in section 4 according to DIN EN ISO 2433 / ASTM D5125): 130 s. The determination of the size of the particles by diffraction of the light using the Mastersizer laser granulometer shows that the particle size is very much less than 1 μm, which confirms the emulsification of all the polyamide-imide resin. . COMPARATIVE EXAMPLE 2: Semifinished aqueous composition (SFC2): Preparation of an aqueous SFC2 semi-finished composition based on a heterocyclic polymer whose d90 is greater than 40 μm, without polar aprotic solvent or amine. An aqueous semi-finished SFC2 composition is prepared comprising the following compounds, their respective amounts being indicated below: Polyamide-amic acid (35.5% ES): 458.9 g Demineralized water: 541.1 g TOTAL: 1000 To produce the aqueous semi-finished SFC2 composition, the procedure is as in Example 1 according to the invention. The properties of the aqueous composition SFC2 thus obtained are as follows: theoretical solids content: 16.3%, dry extract measured in the composition: 16.2%, This is a cream-white suspension. - The pH of this composition is between 3 and 4. - SFC2 decant composition in one day. The determination of the size of the particles by diffraction of the light using the Mastersizer laser granulometer shows that a principal peak at d50 centered on an average diameter of approximately 20 μm and a d90 of approximately 48 is obtained. 15 pm.
    [0032] COMPARATIVE EXAMPLE 3: Semifinished aqueous composition (SFC3): Preparation of an aqueous SFC3 semi-finished composition based on heterocyclic polymer, without polar aprotic solvent and with an amine. An aqueous SFC3 semifinished composition is prepared comprising the following compounds, their respective amounts being indicated below: Polyamide-amic acid (35.5% ES): 149.0 g Triethylamine: 26.0 g - Demineralized water: 710.0 g TOTAL: 885.0 g To produce the aqueous semi-finished SFC3 composition, the following procedure is followed: water, polyamide-amic acid powder and amine are introduced into a reactor; the mixture obtained is stirred, then heated to a temperature of between 50 and 85 ° C .; the water / amine weight ratio is approximately 97/3. The weight percentage of amine in the SFC3 composition is 2.9%. The proportion of polar aprotic solvent in the SFC3 composition is less than 1% by weight relative to the total weight of the composition. The properties of the aqueous composition SFC3 thus obtained are as follows: 25 - theoretical solids content: 6.0% - dry extract measured in the composition: 6.1% - This is a very fluid and white emulsion opalescent. - The pH of the composition is between 10 and 11. - Viscosity (in section 2.5 according to DIN EN ISO 2433 / ASTM D5125): 30 50 s; after aging at 40 ° C, the SFC3 semifinished composition is still stable after 60 days of storage, and the evolution of the viscosity over time is less than 20%. The determination of the size of the particles by diffraction of the light using the Mastersizer laser granulometer shows that the particle size is very much less than 1 μm, which confirms the emulsification. of the totality of the polyamide-amic acid resin. EXAMPLE 5: Inner aqueous composition according to the invention (P1): Preparation of an aqueous primer composition according to the invention P1 starting from the semifinable composition SF1 of Example 1. An aqueous composition is produced of primary primer P1 containing the following compounds, their respective amounts being indicated below: - PTFE dispersion: 33.3 g - Carbon black dispersion: 3.8 g - SF1 semi-finished composition (16, 3% solids content): 30.0 g - N-formylmorpholine: 9.9 g 15 - Nonionic surfactant system: 5.6 g - Colloidal silica: 12.0 g - NH4OH: 0.8 g - Water demineralized: 4.6 g - Total: 100.0 g With regard to the non-toxic polar aprotic solvent in the composition P1, the content of NFM is 9.9% by weight relative to the total weight of the composition P1 . With regard to the polar aprotic solvent toxic in the composition P1, the NMP content is less than 0.7% by weight relative to the total weight of the composition P1; the NMP comes from the semi-finished SF1 composition. The proportion of fluororesin in the dry P1 primer composition is of the order of 66.3% by weight relative to the total dry weight of the composition P1. The relative weight content of polyamide-amic acid / PTFE is about 20:80. The properties of the primer composition P1 thus obtained are: theoretical solids content in the composition: 30.1% - viscosity (in section 2.5 according to DIN EN ISO 2433 / ASTM D5125): 48 s 3 0 2 2 EXAMPLE 6: Aqueous primer composition according to the invention (P2): Preparation of an aqueous primer composition according to the invention P2 from the aqueous semifinable composition SF2 of Example 2.
    [0033] An aqueous P2 primer composition was prepared comprising the following compounds, their respective amounts being indicated below: PTFE dispersion: 36.1 g Carbon black dispersion: 4.1 g semi-finished SF2 (16.3% solids content): 34.1 g - Nonionic surfactant system: 6.0 g - Colloidal silica: 13.0 g - NH4OH: 0.8 g - Demineralized water: 5 , 9 g Total: 100.0 g For the non-labeled polar aprotic solvent in the composition P2, the NFM content is 3.3% by weight relative to the total weight of the composition P2; the NFM comes from the semi-finished SF2 composition.
    [0034] With regard to the polar aprotic solvent labeled in the composition P2, the NMP content is less than 0.8% by weight relative to the total weight of the composition P2; the NMP comes from the semi-finished SF2 composition. The content of fluorinated resin in the dry P2 primary composition is of the order of 66.6% by weight relative to the total dry weight of the composition P2. The relative weight content of polyamide-amic acid / PTFE is about 20:80. The properties of the P2 primary composition thus obtained are as follows: theoretical solids content in the composition: 32.9% - viscosity (in section 2.5 according to DIN EN ISO 2433 / ASTM D5125): 51 s 3 EXAMPLE 7: Inner aqueous composition according to the invention (P3): Preparation of an aqueous primer composition according to the invention P3 from the SF3 semi-finished composition of Example 3 .
    [0035] An aqueous P3 primer composition was prepared comprising the following compounds, their respective amounts being indicated below: PTFE dispersion: 33.2 g Carbon black dispersion: 3.8 g semi-finished SF3 (16.3% solids content): 29.1 g - Dimethylsulfoxide: 10.1 g - Nonionic surfactant system: 5.6 g - Colloidal silica: 11.9 g - NH4OH: 0, 8 g 15 - Demineralized water: 5.5 g - Total: 100.0 g With regard to the polar aprotic solvent not labeled in the composition P3, the DMSO content is 10.1% by weight relative to the total weight of the composition P3.
    [0036] With regard to the polar aprotic solvents labeled in the composition P3, the NMP content is less than 0.7% by weight and the CIP content is 3.1% by weight relative to the total weight of the composition P3. ; NMP and NEP come from the SF3 semi-finished composition. The content of fluorinated resin in the dry P3 primer composition is of the order of 66.6% by weight relative to the total dry weight of the composition P3. The relative weight content of polyamide-amic acid / PTFE is about 20:80. The properties of the P3 primer composition thus obtained are as follows: 30 - theoretical solids content in the composition: 30.0% - viscosity (in section 2.5 according to DIN EN ISO 2433 / ASTM D5125): 49 s 3 EXAMPLE 8: Inner aqueous composition according to the invention (P4): Preparation of an aqueous primer composition according to the invention P4 from the SF2 semi-finished composition of Example 2 and a semifinished composition comprising PES.
    [0037] Firstly, an aqueous PES-based semi-finished composition comprising the following compounds, their respective amounts being indicated below: Polyethersulfone (100% dry extract): 119.1 g 10 - Water demineralized: 625.0 g - TOTAL: 744.1 g To produce the aqueous PES-based semi-finished composition, an initial polyethersulfone powder having a particle size of from 15 μm to 10 mm is used, and more particularly d90 between 40 and 60 pm and a d50 between 20 and 40 pm. The suspension of the PES comprises a grinding stage, the grinding being carried out in a Discontimill® brand ball mill at room temperature to reduce the size of the PES particles.
    [0038] The procedure is as follows: the polyethersulfone powder is introduced into the mill; then the demineralised water is added to the mill; and finally - the grinding step is carried out. The properties of the aqueous composition based on PES thus obtained are as follows: theoretical solids content: 16.0%, dry extract measured in the composition: 16.2%; this is a suspension of white color opaque. - The pH of this composition is between 6 and 7. 30 - Viscosity (in section 4 according to DIN EN ISO 2433 / ASTM D5125)> 30 s: after aging at 40 ° C, the composition based on PES is still stable after 60 days of storage, and the evolution over time of the viscosity is less than 20%. The determination of the size of the particles by diffraction of light using the Mastersizer laser granulometer shows that a principal peak in d50 is obtained centered on a mean diameter of 5 to 6 μm. and a d90 of 19 pm, which confirms the suspension of all the powder.
    [0039] An aqueous primer P4 primer composition is then prepared comprising the following compounds, their respective amounts being indicated below: PTFE dispersion: 37.6 g Carbon black dispersion: 2.8 g Composition SF2 semi-finished product (16.3% solids content): 21.9 g - PES-based semi-finished composition (16.0% solids content): 12.5 g - N-formylmorpholine: 7.2 g - Nonionic surfactant system: 4.2 g 15 - Colloidal silica: 9.0 g - NH 4 OH: 0.5 g - Demineralized water: 4.3 g - Total: 100.0 g 20 Weight ratio polyamide-amic acid / polyethersulfone is about 64/36. As regards the non-labeled polar aprotic solvent in the composition P4, the content of NFM is 9.3% by weight relative to the total weight of the composition P4.
    [0040] With regard to polar aprotic solvents labeled in the composition P4, the NMP content is less than 0.5% by weight relative to the total weight of the composition P4; the NMP comes from the semi-finished SF2 composition. The content of fluorinated resin in the composition of dry P4 primer is of the order of 70% by weight relative to the total dry weight of the composition P4. The relative weight content of polyamide-amic acid and polyethersulfone / PTFE is about 20:80.
    [0041] The properties of the P4 primer composition thus obtained are as follows: theoretical solids content in the composition: 32.1% - viscosity (in section 2.5 according to DIN EN ISO 2433) ASTM D5125): 49 s EXAMPLE 9: Aqueous primer composition according to the invention (P5): Preparation of an aqueous primer composition according to the invention P5 from the SF4 semi-finished composition of Example 4 .
    [0042] An aqueous primer P5 primer composition is prepared comprising the following compounds, their respective amounts being indicated below: PTFE dispersion: 33.3 g Carbon black dispersion: 3.8 g 15-Semi composition -finite SF4 (17.3% dry extract): 28.5 g - N-formylmorpholine: 9.9 g - Nonionic surfactant system: 5.6 g - Colloidal silica: 12.0 g - NH4OH: 1 , 6 g - Demineralized water: 5.3 g - Total: 100.0 g With regard to the non-toxic polar aprotic solvent in the composition P5, the content of NFM is 12.7% by weight relative to the weight Total of the composition P5. With regard to the toxic polar aprotic solvent in the composition P5, the NMP content is less than 0.3% by weight relative to the total weight of the composition P5; the NMP comes from the SF4 semi-finished composition.
    [0043] The proportion of fluororesin in the dry P5 primer composition is of the order of 66.2% by weight relative to the total dry weight of the composition P5. The relative weight content of polyamide-amic acid / PTFE is about 20:80.
    [0044] The properties of the P5 primer composition thus obtained are as follows: theoretical solids content in the composition: 30.2% - viscosity (in section 2.5 according to DIN EN ISO 2433 / ASTM D5125): 58 sec COMPARATIVE EXAMPLE 4: Aqueous Primer Composition (PC1): Preparation of an aqueous PC1 primer composition from the SFC1 semifinable composition of Comparative Example 1. Hereinafter: PTFE Dispersion: 30.5 g Carbon black dispersion: 3.5 g - SFC1 semi-finished composition (9.5% solids content): 47.2 g Nonionic surfactant system: 5.1 g Colloidal silica: 11.0 g NH4OH : 1.4 g Demineralized water: 1.3 g - Total: 100.0 g The amine content in the PC1 primary composition of 1.5% by weight relative to the total weight of the composition PC1; the amine comes from the SFC1 semi-finished composition.
    [0045] With regard to the polar aprotic solvent labeled in the PC1 composition, the CIP content is 16.5% by weight relative to the total weight of the PC1 composition; the NEP comes from the SFC1 semi-finished composition. The content of fluorinated resin in the dry PC1 primer composition is of the order of 66.6% by weight relative to the total dry weight of the PC1 composition. The relative weight content of polyamide-amic acid / PTFE is about 20:80.
    [0046] An aqueous composition of PC1 primer is prepared comprising the following compounds, their respective amounts being indicated. The properties of the PC1 primer composition thus obtained are as follows: theoretical solids content in the composition: 27.6% - viscosity (in section 2.5 according to DIN EN ISO 2433 / ASTM D5125): 55 s COMPARATIVE EXAMPLE 5: Aqueous primer composition (PC2): Preparation of an aqueous composition of PC2 primary from the SFC2 semi-finished composition of Comparative Example 2.
    [0047] An aqueous PC2 primer composition was prepared comprising the following compounds, their respective amounts being indicated below: PTFE dispersion: 36.9 g carbon black dispersion 4.2 g 15 semi composition -finite SFC2 (16.3% solids content): 33.6 g - N-ethylpyrrolidone: 2.6 g - Nonionic surfactant system: 6.2 g - Colloidal silica: 13.3 g - NH4OH: 1 , 7 g. Demineralized water: 1.5 g. Total: 100.0 g. For polar aprotic solvents labeled in the PC2 composition, the NMP content is less than 0.8 wt. in CIP is 2.6% by weight relative to the total weight of the composition PC2; the NMP comes from the semi-finished SFC2 composition. The content of fluorinated resin in the dry PC2 primer composition is of the order of 66.6% by weight relative to the total dry weight of the PC2 composition. The relative weight content of polyamide-acid amide / PTFE is about 20:80. The properties of the PC2 primer composition thus obtained are as follows: theoretical solids content in the composition: 33.5% - viscosity (in section 2.5 according to DIN EN ISO 2433 / ASTM D5125): 55% COMPARATIVE EXAMPLE 6: Aqueous Primer Composition (PC3): Preparation of an aqueous PC3 primer composition from the SF1 semifilm composition of Example 1.
    [0048] An aqueous PC3 primer composition was prepared comprising the following compounds, their respective amounts being indicated below: PTFE dispersion: 37.5 g Carbon black dispersion: 4.3 g semi-finished SF1 (16.3% solids content): 34.1 g - Nonionic surfactant system: 6.3 g - Colloidal silica: 13.5 g - NH4OH: 1.8 g - Demineralized water: 2 , 5 g Total: 100.0 g With regard to the polar aprotic solvent labeled in the PC3 composition, the NMP content is less than 0.8% by weight relative to the total weight of the composition PC3; the NMP comes from the semi-finished SF1 composition. The content of fluorinated resin in the dry PC3 primer composition is of the order of 66.6% by weight relative to the total dry weight of the PC3 composition. The relative weight content of polyamide-amic acid / PTFE is about 20:80.
    [0049] The properties of the PC3 primer composition thus obtained are as follows: theoretical solids content in the composition: 34.0% - viscosity (in section 2.5 according to DIN EN ISO 2433 / ASTM D5125): 51 seconds COMPARATIVE EXAMPLE 7: Aqueous Primer Composition (PC4): Preparation of an aqueous PC4 primer composition from the SFC3 semifinable composition of Comparative Example 3.
    [0050] An aqueous PC4 primer composition was prepared comprising the following compounds, their respective amounts being indicated below: PTFE dispersion: 23.6 g Carbon black dispersion 2.7 g 10 Semi composition -finished SFC3 (6% solids content): 59.2 g - Nonionic surfactant system: 4.0 g - Colloidal silica: 8.5 g - NH4OH: 1.2 g - Demineralized water: 0.8 g Total: 100.0 g The amine content in the PC4 primer composition is 1.7% by weight relative to the total weight of the PC4 composition; the amine comes from the SFC3 semi-finished composition.
    [0051] With regard to the polar aprotic solvent labeled in the PC4 composition, the NMP content is less than 0.5% by weight relative to the total weight of the PC4 composition; the NMP comes from the SFC3 semi-finished composition.
    [0052] The content of fluorinated resin in the dry PC4 primer composition is of the order of 66.6% by weight relative to the total dry weight of the PC4 composition. The relative weight content of polyamide-amic acid / PTFE is about 20:80. The properties of the PC4 primer composition thus obtained are the following: - theoretical solids content in the composition: 21.4% - viscosity (in section 2.5 according to DIN EN ISO 2433 / ASTM D5125): 41 s 3022552 RESULTS OF THE TESTS CARRIED OUT The aqueous semi-finished and primer compositions previously described are listed in Table 1 below. The coatings obtained from these different compositions are subjected to adhesion tests of the primer on the substrate and to the staining test. The coloring of the visually appreciated coating makes it possible to validate that the formulations made according to the invention exhibit null yellowing at low acceptable levels compared with traditional formulations incorporating amines. The adhesion of the coating is ensured when the size of the powder is in accordance with the invention. Table 1 S Composition of SF1 SF2 SF3 SF2 + SF to SF4 SFC1 SFC2 SF1 SFC3 ME semi-finished basis of PES I _ FINI Example Ex.1 Ex.2 Ex.3 - Ex.4 Ex.Comp.1 Ex.Comp. 2 Ex.1 Ex.Comp.3 Type of resin PAI powder PAI powder PAI powder PA PESI powder powder powder PAI solvent PAI powder PAI powder PAI powder PAI e Type of amine 0 0 0 0 0 TEA = 3.3% 0 0 TEA = 2.9% Size of d90 <20pm d50 <10pm d90 <20pm d50 <10pm d90 <20pm d90 <20pm d90 <20pm emulsion d90> 20pm d50> 10pm d90 <20pm d50 <10pm emulsion particles of d50 <10pm d50 < 10pm d50 <10pm resin Polar aprotic solvent NMP <2.3% NMP <2.3% NMP <2.3% in SF2 NMP <1% NEP = 35 `) / 0 NMP <2.3% NMP <2.3 `) / 0 NMP <1`) / 0 NFM = 9.7% NEP = 10.6% NMP <2.3% - NFM = 9.7% NFM = 9 9% 'PR Composition of P1 P2 P3 P4 P5 PC1 PC2 PC3 PC4 I Primary MAYOR Example Ex.5 Ex.6 Ex.7 Ex.8 Ex.9 Ex.Comp.4 Ex.Comp 5 Ex.Comp.6 Ex.Comp.7 Aprotic solvent NFM = 9.9% NFM = 3.3% DMSO = 10.1 NFM = 9.3% NFM = 12.7% 0 0 0 0 polar no% labeled Polar aprotic solvent labeled NMP <0.7 YoNMP <0, 8 `) / 0 NMP <0'7% NMP <0.5`) / 0 NMP <0.3 `) / 0 NEP = 16.5`) / 0 NNMEpP <2 °, ': 0 ° // ° NMP <0.8 `) / 0 NMP <0.5`) / 0 NEP-3.1% TE Coloring of the LOW LOW LOW LOW LOW LOW LOW LOW LOW S COATING YELLOWING YELLOW T NO NO S acceptable acceptable Adhesion test Excellent Excellent Good Excellent Excellent Excellent Bad Bad Excellent on smooth Alu substrate
    权利要求:
    Claims (10)
    [0001]
    REVENDICATIONS1. An aqueous composition for amine-free coating comprising at least one heterocyclic polymer, characterized in that the heterocyclic polymer is in the form of a powder having a d90 of less than or equal to 20 μm.
    [0002]
    2. coating composition according to claim 1, characterized in that it comprises at most 15% by weight of solvent relative to the total weight of the coating composition.
    [0003]
    3. A coating composition according to any one of the preceding claims, wherein the heterocyclic polymer is selected from the group consisting of polyimides (PI), polyamideimides (PAI), polyetherimides (PEI), polyamide-amino acids and their mixtures.
    [0004]
    The coating composition according to any one of the preceding claims, further comprising at least one aromatic polymer having an acid number of 0 mg KOH / g and which is in powder form having a lower d90. or 20 μm, the relative weight content of the heterocyclic polymer with respect to the aromatic polymer in the coating composition being greater than 50:50 and less than 100: 0.
    [0005]
    The coating composition according to claim 4, wherein said aromatic polymer is selected from the group consisting of polyethersulfones (PES), polyether ether sulfones (PEES), polyphenylsulfones (PPSU), phenylene polysulfides (PPS), polyetheretherketones ( PEEK), polyetherketones (PEK), polyetherketonecetones (PEKK), polyetheretherketoneketones (PEEKK), polyetherketoneetherketoneketones (PEKEKK) and derivatives and mixtures thereof. 302 2 5 5 2 37
    [0006]
    6. Aqueous composition of non-stick coating free of amine, characterized in that it comprises an aqueous coating composition according to any one of the preceding claims and at least one fluorocarbon resin. 5
    [0007]
    The release coating composition of claim 6 comprising from 2 to 20% by weight of solvent based on the total weight of the release coating composition. 10
    [0008]
    8. Non-stick coating composition according to any one of claims 6 and 7, characterized in that it comprises at most 1% by weight of polar aprotic solvent toxic relative to the total weight of the release coating composition. 15
    [0009]
    9. Process for the preparation of an aqueous composition for amine-free coating according to any one of claims 1 to 5, characterized in that the process comprises the following steps: a) the provision of at least one heterocyclic polymer under powder form, b) preparing a mixture comprising water and the powder of step a), and c) grinding the mixture from step b) to obtain a ground mixture comprising the polymer heterocyclic powder form having a d90 less than or equal to 20 μm. 25
    [0010]
    A process for preparing an aqueous amine-free release coating composition according to any one of claims 6 to 8, characterized in that the process comprises mixing the aqueous coating composition according to any one of the following: Claims 1 to 5 or as prepared according to the process of Claim 9, with a fluorocarbon resin.
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    同族专利:
    公开号 | 公开日
    FR3022553A1|2015-12-25|
    WO2015193593A1|2015-12-23|
    CN106414628B|2021-04-09|
    US20170152400A1|2017-06-01|
    CN106414628A|2017-02-15|
    US11059981B2|2021-07-13|
    CN106659329A|2017-05-10|
    EP3158018A1|2017-04-26|
    FR3022551A1|2015-12-25|
    BR112016028771A2|2017-08-22|
    EP3158009A1|2017-04-26|
    WO2015193594A1|2015-12-23|
    JP6959713B2|2021-11-05|
    JP6794346B2|2020-12-02|
    US20170158868A1|2017-06-08|
    EP3158018B1|2020-11-18|
    CN106659329B|2020-09-15|
    US10465076B2|2019-11-05|
    JP2017524795A|2017-08-31|
    FR3022551B1|2018-07-06|
    JP2017522436A|2017-08-10|
    FR3022552B1|2016-06-10|
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    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1455723A|FR3022553A1|2014-06-20|2014-06-20|AQUEOUS PHASE PRIMARY COMPOSITION VIA HETEROCYCLIC POLYMERS IN THE FORM OF POWDERS OBTAINED BY MILLING|
    FR1463460A|FR3022552B1|2014-06-20|2014-12-30|AQUEOUS SEMI-FINISH AND ANTI-ADHESIVE COATING PRIMER COMPOSITIONS COMPRISING HETEROCYCLIC POLYMERS|FR1463460A| FR3022552B1|2014-06-20|2014-12-30|AQUEOUS SEMI-FINISH AND ANTI-ADHESIVE COATING PRIMER COMPOSITIONS COMPRISING HETEROCYCLIC POLYMERS|
    CN201580031580.3A| CN106414628B|2014-06-20|2015-06-12|Aqueous intermediate composition and primary composition comprising an anti-adhesive coating of a heterocyclic polymer|
    EP15733828.6A| EP3158018B1|2014-06-20|2015-06-12|Aqueous semi-finished and primary non-stick coating compositions comprising heterocyclic polymers|
    US15/320,523| US10465076B2|2014-06-20|2015-06-12|Aqueous semi-finished and primary non-stick coating compositions comprising heterocyclic polymers|
    JP2017518610A| JP6959713B2|2014-06-20|2015-06-12|Aqueous intermediate compositions containing heterocyclic polymers and non-stick primer coating compositions|
    PCT/FR2015/051570| WO2015193593A1|2014-06-20|2015-06-12|Aqueous semi-finished and primary non-stick coating compositions comprising heterocyclic polymers|
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