MXPA06001470A - Electrostatic composition based on a polyamide matrix - Google Patents

Abstract

The invention relates to a composition based on a polyamide matrix comprising electrically conductive charges and antistatic agents. This composition makes it possible to obtain plastic articles, for example, body parts used in the automobile industry that are well-suited for painting by means of an electrostatic paint deposition process.

Description

ELECTROSTATIC COMPOSITION BASED ON A POLYAMIDE AGLOMERANT The present invention relates to a composition based on a polyamide binder comprising electrically conductive fillers and antistatic agents. The use of this composition makes it possible to obtain plastic articles, such as, for example, body parts in the automotive industry, which have a good ability to be painted by a deposition process. • electrostatic painting.

PREVIOUS TECHNIQUE In many industries, there is a significant demand for parts of polyamide materials. Indeed, these parts are light and can be known and designed more easily than steel or aluminum parts, notably in the automotive industry. However, plastic parts have problems when they want to paint. Thus, for example, in the automotive industry, there are notably three main methods of painting by electrostatic process, that is, by movement of particles under the influence of an electric current. The first called "process by line" refers to a process according to which the part of plastic material is assembled on the vehicle after it has been subjected to the degreasing and galvanization steps followed by a drying step. The part of plastic material and the vehicle are painted immediately and dried by heating. The second, called the "on-line" process, refers to a process according to which the part of plastic material is assembled on the vehicle at the beginning of the aforementioned process. The plastic parts therefore undergo the following stages of degreasing, galvanization and drying, at temperatures that can exceed 200 ° C. Consequently, for this type of process, it is necessary that the parts of plastic material can withstand higher temperatures. important In a third process, called the "off-line" process, the part of plastic material is painted to be assembled immediately in the vehicle. When electrostatic deposition paint processes are used, poor adhesion of the paint to classical plastic parts is obtained. In effect, the paint is easily torn off and adheres little or does not adhere to the plastic parts. In order to render the plastic parts suitable for painting by an electrostatic paint deposition process, it is known to add conductive charges in the thermoplastic binder. However, the incorporation of these fillers negatively affects certain properties of the plastic materials, such as the mechanical properties. In addition, the incorporation of the conductive fillers significantly increases the viscosity in the molten state of the ermoplastic binders, making them unsuitable for use for certain forming processes of these binders. Thus, there is a need to manufacture and use plastic parts that exhibit high mechanical properties, such as good shock resistance, and a good ability to be painted by an electrostatic paint deposition process.

BRIEF DESCRIPTION OF THE INVENTION The applicant has evidenced a composition based on a polyamide binder comprising electrically conductive fillers and antistatic agents. This polyamide composition allows the formation of articles that have a good balance of mechanical properties, thermal and ability to be painted, notably by deposition of paint by an electrostatic process. The plastic parts according to the invention also have a coefficient of linear thermal expansion (CTLE) which is advantageously suitable for the automotive industry. The plastic parts according to the invention also have a good thermal resistance, a good surface appearance and a good propensity for molding. These plastic parts are thus very well suited to electrostatic deposition painting processes, such as the "line", "in line" and "off-line" procedures notably used in the automotive industry. It will further be noted that the composition based on a polyamide binder according to the invention is significantly less viscous in the molten state, compared to a polyamide composition comprising only conductive fillers, which is particularly interesting for certain part manufacturing processes, such as injection molding.

DETAILED DESCRIPTION OF THE INVENTION The present invention has for its first object a composition comprising at least one polyamide binder: at least 2% by weight of electrically conductive fillers; and at least 1% by weight of antistatic agents; percentages by weight expressed with respect to the total weight of the composition. This composition may comprise one or more types of electrically conductive fillers and one or more types of antistatic agents. Preferably, the composition according to the invention is an electrostatic dissipating composition having a surface resistivity comprised between 105 O and 10 11 O, according to the IEC 61340-4-1 standard.

The composition according to the present invention can also have a discharge time greater than or equal to 10 seconds, preferably greater than or equal to 30 seconds, more preferably greater than or equal to 50 seconds, measured according to IEC 61340-5-1. The discharge time can, for example, be measured on a plate (for example, having the following dimensions: 200x150x3 mm) obtained from the composition according to the invention on which a load of 1000 volts (V) is applied. The discharge time corresponds to the time necessary for the electrical voltage on the surface of the plate to pass from 1000 V to 100 V. The parameters of surface resistivity and the discharge time of the composition of the invention are particularly well suited for the obtaining of articles having a good compatibility for the painting and a good compromise of mechanical properties. The composition according to the invention can comprise from 2 to 50% by weight of electrically conductive fillers with respect to the total weight of the composition, preferably from 2 to 30% by weight, even more preferably from 2 to 10% by weight, particularly from 2 to 10% by weight. to 5% by weight. The electrically conductive fillers are preferably chosen from the group comprising: a carbon black, a metal, a graphite, a conductive polymer, a glass and / or a mineral filler coated with a metal layer, and / or their mixture. The glass and / or the mineral fillers can be coated by a layer of metal, such as nickel, aluminum, silver, iron, chromium and / or titanium, for example. The electrically conductive charges may be in the form of a sphere, such as, for example, in the form of a microsphere and / or nanosphere; tubes, for example, in the form of microtubes and / or nanotubes; and / or fibers, as for example, in the form of microfibres and / or nanofibers. These fibers can be cut and / or ground. As the conductive polymer, for example, polyaniline, polypyrrole, polythiophene and / or polyacetylene can be used. Preferably, the conductive filler according to the invention is carbon black. Conductive carbon black is remarkably described in Coal Black Second Edition Revised and Expansed, Science and Technology edited by JB. Donet RC Bansal and MJ Wang, Marcel Dekker Inc. pages 271-275. Preferably, the composition according to the invention comprises from 2 to 10% by weight of carbon black, preferably from 2 to 5% by weight, particularly from 2 to 4% by weight, as electrically conductive fillers, with respect to weight total of the composition. The antistatic agents according to the present invention can also be called dissipative electrostatic agents. Preferably, the composition according to the invention comprises from 1 to 30% by weight of antistatic agents, with respect to the total weight of the composition, even more preferably from 5 to 20% by weight. The antistatic agents may be chosen, for example, from the group comprising the polyether amides, sodium alkylsulfonates, alkylbenzene sulfonates, primary, secondary and tertiary amines, ethoxylated amines, ethoxylated alcohols, monostearate, distearate or glycerol tristearate, and mixtures thereof.

Polyethers are understood as different types of polymers comprising one or more blocks of polyamide and one or more blocks of alkylene polyoxide. Preferably, the polyether amide is a block polymeric compound represented by the formula (I): * -C-PA-C-X-POA-X-t-. where: ^ 1 o1 ^ - n is an integer between 5 and 50; - X represents an oxygen atom or an NH group; POA represents a block of alkylene polyoxide; - PA represents a block of polyamide of which the repeat motif is represented by one of the formulas (lia) or (Ilb): * -. { -C-R1-NH -] - (Ha) * ^ C-R2 ^ C - NH-R3-NH -] - * (llb) wherein: R1, R2, R3 are aromatic or aliphatic radicals comprising 4 to 36 carbon atoms. The block copolymer represented by the formula (I) is a polyether block or a polyetheresteramide. Such compounds are notably marketed by the company Atocina under the name of PEBAX® and the company Ciba under the name Irgastat. It comprises blocks _ of polyamide, and blocks of polyalkylene glycol. The number of blocks of each nature is comprised between 3 and 50. Preferably, between 10 and 15 is understood. The number of blocks is represented by the integer n in formula (I). The polyamide blocks can be represented by one of the formulas (bundle) or (Ilb) represented above. The blocks of the formula (Ha) are polyamides of the type of those obtained by polymerization from lactams and / or amino acids. The polymerization processes of such compounds are known: the anionic polymerization, molten polycondensation, for ple, in a VK tube are also mentioned. The blocks (Hb) are of the type obtained by polycondensation of dicarboxylic acids on the amines. Preferably, X represents an oxygen atom, formula (I) being thus the following: According to the embodiment in which the polyamide block is represented by the formula (Ha), the radical R1 is advantageously chosen from the following radicals: the divalent linear pentyl radical, the polyamide block is then a block of polyamide 6; the divalent non-branched decyl radical (10 carbon atoms), the polyamide block is then a block of polyamide 11; the non-branched divalent radical of undecyl (11 carbon atoms), the polyamide block is then a block of polyamide 12. According to the embodiment where the polyamide block is represented by the formula (Hb), the radical pairs R2 and R3 are advantageously between the following pairs: R2 = divalent linear butyl radical, R3 = divalent linear hexyl radical, polyamide 66 block; - R2 = divalent linear butyl radical, R3 = divalent linear butyl radical, polyamide 4-6 block; - R2 = divalent linear octyl radical, R3 = divalent linear hexyl radical, polyamide block 6-10; The alkylene polyoxide block can be chosen from the blocks of ethylene polyoxide, polythri ethylene oxide, polytetra ethylene oxide. In the case where the block is based on ethylene polyoxide, it can comprise propylene glycol motifs at the ends of the block. The average molecular masses of each of the blocks are independent of each other. However, it is preferred that they be close to each other. The average molecular mass of POA blocks is preferably between 1000 and 3000 g / mol). The average molecular mass of the PA blocks is advantageously between 1000 and 3000 g / ml The compound of the formula (I) can be obtained by catalyzed reaction between the macromolecular polyamide chains of which the terminal functions are carboxylic acid functions and chains of polyether diols, ie macromolecular chains of alkylene polyoxide of which the terminal functions are alcohol functions, for ple, polyethylene glycol chains with alcohol endings. The blocks can be catalyzed by tetraalkyl ortitanatos or zirconyl acetate According to a particular embodiment of the invention, the modifying compounds of the formula (I) have a melting temperature greater than 150 ° C, preferably between 150 and 250 ° C. The polyamide binder according to the invention is generally comprised of at least one (co) polyamide selected from the group comprising: (co) polyamide 6; 4; eleven; 12, 4.6; 6.6; 6.9; 6.10; 6.12; 6.18; 6.36; 6 (T); 9 (T); 6 (1); MXD6; its copolymers and / or mixtures. Mention may be made, for example, of semi-Christian aliphatic or amorphous polyamides, such as aliphatic polyamides, semi-aromatic polyamides and, more generally, linear polyamides obtained by polycondensation between an aliphatic or aromatic saturated diacid and an aromatic saturated primary diamine or aliphatic, the polyamides obtained by condensation of a lactam, an amino acid or the linear polyamides obtained by condensation of a mixture of different monomers. These polyamides can be, for example, hexamethylene polyadipamide, polieftalamides obtained from terephthalic and / or isophthalic acids, copolyamides obtained from caprolactam, and one or more monomers generally used for the manufacture of polyamides, such as atypical acid, terephthalic acid, and / or hexamethylene diamine. Polyamide 6 (T) is a polyamide obtained by polycondensation of terephthalic acid and hexamethylene diamine. The polyamide 9 (T) is a polyamide obtained by polycondensation of terephthalic acid and of a diamine comprising 9 carbon atoms. . The polyamide 6 (1) is a polyamide obtained by polycondensation of isophthalic acid and hexamethylene diamine. Polyamide MXD6 is a polyamide obtained by polycondensation of atypical acid and metaxylylene diamine. The composition may comprise one or more (co) polyamides obtained in mixture or in copolymers, for example. The polyamide binder can notably be a polyamide comprising cracked macromolecular chains or H, and eventually the linear macromolecular chains. Polymers comprising such cracked macromolecular chains or H are, for example, described in FR2743077, FR2779730, US5959069, EP0632703, EP0682057 and EP0832149. According to another particular variant of the invention, the polyamide binder of the invention can be a polymer of static tree type, preferably a copolyamide having a static tree structure. These polyamides with a static tree structure and their production processes are remarkably described in WO99 / 03909. The thermoplastic binder of the invention can also be a composition comprising a linear thermoplastic polymer and a cracked thermoplastic polymer, H and / or tree, such as those described above. The thermoplastic binder of the invention may also comprise a hyperamidated copolyamide of the type described in WO00 / 68298. The thermoplastic binder of the invention may also comprise any combination of linear thermoplastic polymer, cracked, H, tree, hyperamidated copolyamide as described above. According to a particular characteristic of the invention, the polyamide binder of the composition is constituted by a mixture of a polyamide with one or more other polymers, preferably of the (co) polyamide type. A mixture of (co) polyamide with at least one polymer selected from the group comprising: polyphenylene ether (PPE), polyvinyl chloride (PVC), acrylonitrile-but-adiene-styrene polymer (ABS), polyethylene (PE) ), polypropylene (PP), polyethylene terephthalate (PET), and / or polybutylene terephthalate (PBT), is also contemplated. The polyamide composition according to the invention may comprise reinforcing and / or filling fillers preferably chosen from the group comprising the fibrous fillers, such as glass fibers, metal fibers, carbon fibers; mineral fillers such as clay, kaolin, olastonin, mica, talcum and glass beads; finely dispersible reinforcing nanoparticles, such as montmorillonite; or of hardening material. The rate of incorporation of these charges is in accordance with the standards in the field of composite materials. It can be treated, for example, of a loading rate of 1 to 70% by weight, preferably 10 and 60% by weight, based on the total weight of the composition. The polyamide composition according to the invention can also comprise at least one impact modifier chosen, for example, from the group comprising: ethylene propylene (EP) optionally grafted with maleic anhydride, the ethylene propylene diene terpolymer (EPDM) ) optionally grafted with maleic anhydride, elastomer copolymers such as maleic styrene anhydride (SMA) for example, ultra-low density polyethylene (ÜLDPE), linear low density polyethylene (LLDPE), styrene-butadiene (SBS and SBR), styrene-ethylene-butadiene styrene (SEBS), polypropylene (PP), acrylic elastomers (such as polyacrylic elastomers), copolymer and terpolymers of ethylene with acrylic or methacrylic derivatives and / or with acetate of vinyl, iono eros, acrylonitrile-butadiene-styrene terpolymer (ABS) and acrylic terpolymer 11 co-styrene-acrylonitrile (ASA). The impact resistance modifiers may optionally comprise grafted groups such as maleic anhydride, for example. The impact resistance modifiers according to the invention may also be combinations, mixtures, homopolymers, copolymers and / or terpolymers of compounds mentioned above. The impact resistance modifiers are chosen by the person skilled in the art for their compatibility with the polyamide binder. The polyamide composition according to the invention can also comprise one or more additives usually used by a person skilled in the art in thermoplastic compositions, notably used for the manufacture of molded articles. Thus, mention may be made, as an example, of additives, thermal stabilizers, flame retardants, molding agents such as calcium stearate, Ü.V. stabilizers, antioxidants, lubricants, abrasion reducers, pigments, dyes, plasticizers, marking promoters. with lasers, waxes or resilience modifiers. By way of example, antioxidants and heat stabilizers are, for example, alkali halides, copper halides, sterically filled phenolic compounds, organic phosphites and aromatic amines.

The present invention also relates to a process for preparing a polyamide composition as defined above, in which at least 2% by weight of electrically conductive fillers and at least 1% by weight of antistatic agents are mixed with a polyamide binder, optionally in the molten state. The mixing can be carried out in the molten state, for example, in a single or bi-screw extruder, or by mixing without passing into the molten state, for example, in a mechanical mixer. The compounds can be introduced simultaneously or successively. All means known to those skilled in the art relate to the introduction of different compounds of a thermoplastic composition that can be used. An extrusion device is generally used in which the material is heated, subjected to a shearing force, and vehicle. Such devices are well known to the person skilled in the art. The composition according to the invention, when prepared with the aid of an extrusion device, can be packaged in the form of granules.

The mixing of the electrically conductive fillers and antistatic agents can be effected previously, for example, by continuous or discontinuous mixing. To do this, you can use, for example, a Banbury mixer. It is also possible to add to the polyamide binder, a concentrated mixture, preferably based on polyamide, comprising the electrically conductive fillers and / or the antistatic agents, prepared for example, according to the method described above. This master mix can, for example, be carried out by pre-mixing different compounds. Thus, the present invention also relates to a process for preparing a polyamide composition as described preferably, in which at least one polyamide binder is mixed with: a concentrated mixture based on a thermoplastic binder comprising at least one 20% by weight of electrically conductive filler, and - at least 1% by weight of antistatic agents. The mixture may comprise, for example, from 20 to 50% by weight of the electrically conductive fillers, such as carbon black. This master mix is based on a thermoplastic binder, for example, chosen from the group comprising: one (co) polyamide, an ethylene / vinyl acetate copolymer (EVA), an ethylene / acrylic acid (EAA), a polyethylene (PE), a polypropylene (PP), its copolymers and / or mixtures. It has been observed that the masterbatch can also comprise antistatic agents according to the invention. Numerous methods of mixing (co) polyamides of the invention with reinforcing and / or filling fillers, impact modifiers and / or additives can be contemplated. These can, for example, be introduced in a mixture with the (co) polyamide in the molten state before the production of granules. Certain of these fillers, agents and / or additives can also be added during the polymerization of (co) polyamide. The present invention also relates to the process of manufacturing an article, by the formation of a composition according to the invention by a process chosen from the group comprising an extrusion process, such as extrusion of sheets and films, molding, such as molding by compression, and injection, such as injection molding. The articles according to the invention can, for example, automotive parts, in particular body parts, tubes for the transport of fluids or gas, containers, coatings, films and / or plastic container covers. The present invention also relates to the process of applying paint by electrostatic deposition on an article, characterized in that an article of the invention as described above is used in this process. The application of the paint on the article can be effected, for example, by vaporization or immersion. Generally, a process of applying paint by electrostatic deposition on an article comprises at least the following steps: Treatment in cathoresis of the article at temperatures between 150 and 250 ° C, Application of an effect (primer) by electrostatic vaporization, Application of the painting by electrostatic vaporization. Each vaporization step can be followed by the heating stage (s) at temperatures between 100 and 200 ° C, and the cooling stage (s). The present invention also relates to an article painted by a process of applying paint by electrostatic deposition. Other details or advantages of the invention will appear more clearly in view of the examples provided below only by way of indication. EXPERIMENTAL PART Materials used: PA 66: polyamide 66 with a relative viscosity 2.7 (according to ISO 307 using sulfuric acid as a solvent) marketed by the company Rhodia Engineering Plastics under the name Technyl® 27 A00. PA 6: polyamide 6 of the relative viscosity 2.7 (according to ISO 307 using as solvent sulfuric acid) marketed by the company Rhodia Engineering Plastics under the name ASN 27 S. Elastomer: EPR-g-MA: Ethylene-propylene copolymer comprising grafted maleic anhydride, having a density of 0.87 g / ml (measured according to ASTM D792) and MFR of 23 (measured according to ASTM D1238, at 280 ° C / 2.16 kg). Conductive carbon black, marketed by AKZO under the name Ketjen Black 600®. - Polyetherramide: multisegment block copolymer comprising 60% by weight of blocks of polyamide 6 and 50% by weight of blocks of polyethylene glycol, X corresponding to an oxygen atom; of which the average molecular mass of each block is approximately 1500 g / ml. Melting point: 204 ° C according to ASTM D3418. - Wollastonite: calcium silicate having a granulometry of less than 10 μm and a shape factor of 5, surface treatment with a coupling agent. Mica: mica of muscovite type ground, having an average granulometry, expressed in D50 less than or equal to 40 μm, and an apparent density of 450 g / l. - Others: corresponds to a mixture of color stabilizer and lubricants (calcium stearate). - Master mix MB: EVA-based mixture comprising 30% black. Ketjen Black 300® conductive carbon, sold by the company Iridi Color Sri under the name MBÜN NIRO N129. Example 1: Preparation of compositions Compositions based on polyamide are manufactured by mixing different compounds mentioned below through a twin screw extruder. The compositions, the compounds used and their amounts are mentioned in Table 1: Table 1 The percentages of different compounds are expressed as the total weight of the composition. The properties are measured as follows: - MFI (melt flow index) melt flow index according to ISO 1133 at 275 ° C with a load of 5 kg. - Choc Charpy cut according to ISO 179 / leA at 23 ° C. - Elongation at break according to ISO 527 at 23 ° C. - Voltage module according to ISO 527 at 23 ° C. - HDT (Heat deformation temperature) according to ISO 75Be with a load of 0.45 N / mm2. Surface resistivity according to IEC 61340-4-1. The measurement is made on an injection molded plate (200x150x3 mm) when placing the probes of an apparatus to measure the resistance of the Metriso 2000 ESD brand at a distance of 1 cm from each other. A voltage of 100 volts is applied and the surface resistivity of the plate is measured. The measurement is made in one part at a temperature of approximately 23 ° C and a relative humidity of 50%. Adhesion of the paint by electrostatic deposition: a plate is injection molded from the previous compositions. The application of the paint on the plates is carried out by an "on-line" process of cataphoresis painting in seven stages: Stage 1: simulation of layer e (cataphoresis treatment) at 185 ° C for 30 minutes. Stage 2: cooling for 20 minutes. Stage 3: application of the "primer" BASF PMR85 by electrostatic vaporization. Stage 4: heating at 160 ° C for 30 minutes. Stage 5: cooling for 20 minutes. Stage 6: application of a white paint by electrostatic vaporization. Stage 7: cooling for 20 minutes. A bad adhesion of the paint by electrostatic deposition (observed in the previous table) is observed if an orange peel appearance is observed, a lack of paint and / or poor adherence of the paint on the plate. Otherwise, a good adhesion of the paint is observed (observed + in the previous table). In the previous table, n means without measuring. Example 2: Preparation of compositions The polyamide-based compositions are manufactured by mixing different compounds mentioned below through a twin-screw extruder. The compositions, compounds used and their amounts are mentioned in table 2: The percentages of different compounds are expressed by weight with respect to the total weight of the composition.

Claims (19)

1. CLAIMS 1. Composition comprising a polyamide binder, characterized in that it comprises: - at least 2% by weight of electrically conductive fillers; and at least 1% by weight of antistatic agents; percentages by weight expressed with respect to the total weight of the composition. Composition according to claim 1, characterized in that it has a surface resistivity comprised between 105 O and 1011 O, measured according to IEC 61340-4-1. Composition according to any one of claims 1 to 2, characterized in that it has a discharge time greater than or equal to 10 seconds measured according to IEC 61340-5-1. Composition according to any of claims 1 to 3, characterized in that it comprises from 2 to 50% by weight of electrically conductive fillers with respect to the total weight of the composition. Composition according to any of claims 1 to 4, characterized in that the electrically conductive fillers are selected from the group comprising: a carbon black, a metal, a graphite, a conductive polymer, a glass and / or a mineral filler coated with a metal layer, and / or its mixture. Composition according to any of claims 1 to 5, characterized in that it comprises from 2 to 10% by weight of carbon black as electrically conductive fillers, with respect to the total weight of the composition. Composition according to any of claims 1 to 6, characterized in that it comprises from 1 to 30% by weight of antistatic agents with respect to the total weight of the composition. 8. Composition according to any of claims 1 to 7, characterized in that the antistatic agents can be chosen from the group comprising polyether amide, sodium alkylsulfonate, alkylbenzene sulfonate, primary, secondary or tertiary amines, ethoxylated amine, ethoxylated alcohol, monostearate, distearate or tristearate glycerol, and its mixtures. 9. Composition according to any of claims 1 to 8, characterized in that the antistatic agent is a polyether amide represented by the formula (I): in which: - n is an integer between 5 and 50; - X represents an oxygen atom or an NH group; POA represents a block of alkylene polyoxide; - PA represents a block of polyamide of which the repeat motif is represented by one of the formulas (bundle) or (Ilb): * -f-R1-NH-j- (l «a) * -HAR2" -0-NH-R3-NH -] - * (llb) in which RJ R 'R- are aromatic or aliphatic radicals comprising 4 to 36 carbon atoms. 10. Composition according to claim 9, characterized in that the radical R1 is a pentyl divalent linear radical. 11. Composition according to any of claims 9 to 10, characterized in that the POA block is a block of ethylene polyoxide. Composition according to any of claims 1 to 11, characterized in that the polyamide binder according to the invention is composed of at least one (co) polyamide selected from the group comprising: (co) polyamide 6; 4; eleven; 12, 4.6; 6.6; 6.9; 6.10; 6.12; 6.18; 6.36; 6 (T); 9 (T); 6 (1); MXD6; its copolymers and / or mixtures. 13. Composition according to any of claims 1 to 11, characterized in that the composition comprises at least one modifier of shock resistance chosen, from the group comprising: ethylene propylene (EP) optionally grafted with maleic anhydride, the ethylene propylene diene terpolymer (EPDM) eventually grafted with maleic anhydride, elastomer copolymers such as maleic styrene anhydride (SMA), ultra-low density polyethylene (ÜLDPE), linear low density polyethylene (LLDPE), styrene-butadiene (SBS and SBR), styrene-ethylene-butadiene styrene (SEBS), polypropylene (PP), acrylic elastomers (such as polyacrylic elastomers), copolymer and terpolymers of ethylene with acrylic or methacrylic derivatives and / or with acetate of vinyl, ionomers, terpolymer acrylonitrile-butadiene-styrene (ABS) and acrylic-styrene-acrylonitrile terpolymer (ASA). 14. Process for preparing a polyamide composition according to any of claims 1 to 13, characterized in that at least 2% by weight of electrically conductive fillers and at least 1% by weight of antistatic agents are mixed with a polyamide binder, optionally in molten state. Process for the preparation of a polyamide composition according to any of claims 1 to 13, characterized in that at least one polyamide binder is mixed with: a concentrated mixture based on a thermoplastic binder comprising at least 20% by weight electrically charged conductive, and - at least 1% by weight of antistatic agents. 16. Process according to claim 15, characterized in that the thermoplastic binder is selected from the group comprising: (co) polyamide, ethylene / vinyl acetate copolymer (EVA), ethylene / acrylic acid (EAA), polyethylene (PE), polypropylene (PP), its copolymers and / or mixtures. 17. Process for manufacturing an article by forming a composition according to any of claims 1 to 13, by a process chosen from the group comprising an extrusion, molding, and injection process. 18. Article obtained by forming a composition according to any of claims 1 to 13. 19. Article according to claim 18, characterized in that it is painted by a paint application process by electrostatic deposition.