ES2631991B1 - FORMULATION OF COAT GEL COAT IN POWDER WITH ELECTRICAL CONDUCTIVITY PROPERTIES - Google Patents

Abstract

Powder gel coat coating formulation with electrical conductivity properties. # A powder gel coat coating formulation and with electrical conductivity properties, characterized in that it comprises: a solid unsaturated polyester resin, a cross-linking agent comprising at least a double carbon-carbon bond, an organic peroxide polymerization initiator, and electrically conductive carbon particles. Process of obtaining the gel coat powder coating formulation by extrusion. Use of the formulation to obtain a conductive gel coat coating and the electrically conductive gel coat coating obtained from this formulation.

Description

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DESCRIPTION

FORMULATION OF COAT GEL COAT POWDER WITH PROPERTIES OF

ELECTRIC CONDUCTIVITY

SECTOR OF THE TECHNIQUE

The present patent application refers to a gel coat, or gel coat, powder coating formulation that includes carbonaceous charges that confer electrical conductivity properties.

BACKGROUND

Plastics in general, and composites in particular, have application in a wide range of sectors where the application of coatings is necessary to obtain electrical conductivity properties, for example in electrostatic painting of plastic parts in the transport sector.

Conductive coatings of electricity are known in the state of the art using different types of conductive charges such as zinc oxide (WO99 / 39839) or metal powders (EP 425 677, US 5,556,576, JP 62-197473, JP 62-018481). In particular, US patent application 2015/0240088 A1 (PPG Industries Ohio, Inc) describes a coating containing carbon graphene particles and a polymeric resin that can be thermoplastic or thermoset.

However, all these formulations of coatings are applied in secondary painting processes after obtaining the piece of composites. So far there are no known formulations of gel coat powder coatings with conductive properties of electricity, that is, formulations that can be applied directly to the mold and allow to obtain the composite part directly with a conductive coating.

Liquid gel coat type coating formulations are a product widely used in the manufacture of composites. We can define the gel coat type coating as the first layer that is applied to the mold prepared for the manufacture of the piece

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(composite), and that constitutes the finish of one of the surfaces of the laminate, providing protection against chemicals, weathering or humidity and giving it specific properties such as electrical conductivity properties.

The gel coat or gel coat type formulations are based on a resin to which additives, pigments and fillers can be added. These formulations can be applied in the mold and partial curing is carried out before applying the reinforcement and injecting the resin that will form the final piece of composite material. The gel coat coating finishes curing during the composite manufacturing process and this is one of the advantages of its application, since the gel coat coating and the resin used to manufacture the composite part react together forming chemical bonds which improves the adhesion between both components.

Currently, the vast majority of liquid formulations to obtain commercially available gel coat coatings comprise a polyester resin. In these formulations there is an essential component, styrene, which is part of the resin components. Styrene acts as a solvent and as a crosslinking agent in gel coat coating formulations and during the polymerization process of the resin part of it is evaporated as a gas. Styrene is classified as a hazardous material for health and the environment, so there is an increasingly restrictive legislation regarding emissions of this component.

Despite the great economic advantage of applying liquid gel coat coating formulations known to date, there are several technological challenges facing the industry:

• Reduction of styrene emissions.

• Reduction in handling toxic / hazardous materials for workers.

• Control of polymerization conditions to ensure the final quality of the parts.

In addition to these challenges directly related to the application of the gel coat coating, the composites industry needs to reduce manufacturing cycle times in order to reach new markets, among others the automotive sector.

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On the other hand, powder coating formulations are known as efficient, resistant, robust and ecological formulations. The use of these formulations for powder coating instead of liquid paints allows reducing emissions and overspray residues.

The first patent we found on a powder coating that is used in "in-mold coating" techniques dates from 1983 and is from DSM resins B.V. Ferro Corporation and Synres Almoco. However, this type of coatings has been used exclusively in the manufacture of composite materials using SMC (sheet molding compound). This process consists of high temperature compression molding (minimum 160 ° C) of a mixture of glass, resin, fillers, additives and catalytic system.

Until now, gel coat type powder formulations were restricted to this process, due to the high cure temperature necessary for coating formation (minimum 160 ° C). At present, there are no powder coat formulations of the gel coat type that can be applied in composites manufacturing processes (RTM or infusion) at temperatures between 110-150 ° C). Additionally, gel coat formulations that have electrical conductivity properties are also unknown.

DESCRIPTION

Brief Description of the Invention

One of the objectives of the present invention is to develop a gel coat or gel coat type formulation, where this formulation is a powder, includes electrically conductive carbon charges and is stable during conventional extrusion. In this way, the formulation of the present invention allows to obtain a gel coat type coating with electrical conductivity properties, preferably at lower temperatures (110-150 ° C) than those used for a conventional powder coating process (160-210 ° C). In addition, both the coating formulation and the gel coat coating obtained therefrom preferably have good storage stability at room temperature.

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Thus, the present patent application refers to a coating formulation, in particular gel coat type characterized in that the formulation comprises:

• a solid resin, preferably powder, of unsaturated polyester, preferably hydroxylated, carboxylated polyester or a combination of both with unsaturation in its chain, where these unsaturated polyesters can be obtained by reaction with olefinically unsaturated di- or polycarboxylic acids or anhydrides, as per example maleic acid or anhydride;

• a crosslinking agent comprising at least one carbon-carbon double bond, preferably blocked isocyanates, amine resins, hydroxyalkylamides and aromatic or aliphatic epoxy resins;

• an organic peroxide polymerization initiator, that is, an organic peroxide capable of generating free radicals; Y

• carbonaceous particles conducting electricity; where the formulation is dust and electricity conductor.

The gel coat formulation of the present invention can be applied on a mold previously prepared to obtain a composite material (also called composites in this patent application) comprising a resin and an electrically conductive gel coat coating. Preferably, a coating with an electrical conductivity between 1 and 10 "12 S / cm.

Preferably, the gel coat coating formulations described in this application have a glass transition temperature (Tg) between 40 ° C and 80 ° C, in order to provide the formulation with the stability necessary for storage.

The coating formulation of the present invention can give rise to thermosetting structures (gel coat or gel coat type) by radical polymerization, where polymerization can take place in the mold prepared for the manufacture of composites, at a cure temperature between 110 -150 ° C, starts only by temperature, and the gel coat application process can be carried out the same equipment used to obtain conventional powder coatings. In this way, the process of obtaining thermostable structures from the powder coating formulation of the present invention can be easily applied using electrostatic powder painting equipment.

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In preferred embodiments of this invention, the thermosetting structure that forms the gel coat coating is obtained by radical polymerization of the unsaturated polyester resin and the cross-linking agent in the presence of an initiator, in particular an organic peroxide. This gel coat formulation is stable at the temperatures at which extrusion is carried out (ie, between 80-100 ° C). Applied on a mold, the formulation has a gelation time of 1 to 30 minutes, when a temperature between 110-150 ° C is reached, depending on the relationship between resin and crosslinking agent, as well as the concentration of organic peroxide. In this invention it has been possible to reach a compromise between the minimum formation temperature of the gel coat coating and the storage stability, since the lower the formation temperature of the coating, the worse the storage stability of the powder at room temperature.

Detailed description of the invention

The coating formulation described in this patent application has advantageous characteristics over other formulations described above. In particular, this formulation is a gel coat formulation that can give rise to thermosetting structures by radical polymerization with a maximum cure temperature between 110 and 150 ° C, and with a gelation time between 1 and 30 minutes applied on a mold a temperature between 100 and 150 ° C. Additionally, the present invention provides a solid and stable gel coat coating formulation during storage, with stability measured on the basis of Tg (Tg between 40 and 80 ° C), without agglomeration or crosslinking; and with one with an electrical conductivity between 1 and 10 "12 S / cm, suitable values to obtain an electrical coating.

Polymers are intrinsically insulating materials. However, thanks to the addition of conductive additives, they can change their electrical properties and can replace metals in a large number of applications. In the market there are different additives developed in order to improve the electrical properties of polymers. However, the present invention relates to the addition of carbonaceous particles among which are carbon blacks, carbon nanotubes, carbon fibers, graphites, graphenes and combinations thereof.

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In a first aspect, the present invention relates to a gel coat, or gel coat, powder and electrically conductive coating formulation, characterized in that it comprises:

- a solid unsaturated polyester resin;

- a cross-linking agent, preferably solid, comprising at least one carbon-carbon double bond;

- an organic peroxide polymerization initiator; Y

- carbonaceous particles conductive of electricity.

This coating formulation allows to obtain solid gel coat coatings, with conductive properties of electricity. Advantageously, these coatings can be obtained at a cure temperature between 110 and 150 ° C.

The formulation described in this patent application is in the solid state, preferably in powder form, more preferably it is a micronized powder and, particularly preferably micronized powder with a particle size between 0.1 and 500 microns although more preferably between 0.1 and 300 microns and more preferably between 0.1 and 100 microns.

The unsaturated polyester resin may be formed by one or more hydroxylated or carboxylated polyesters with at least one unsaturation in their chain. In preferred embodiments of the present invention, the unsaturated polyester solid resin comprises at least one polyester and at least one unsaturated fragment, for example, from the incorporation of maleic anhydride to the polyester structure with a glass transition temperature (Tg) between 0 ° C and 100 ° C, more preferably between 20 ° C and 60 ° C. A melt temperature between 40 ° C and 150 ° C and more preferably between 60 and 100 ° C. Examples of powder resins that can be used are Uracross (XP 757, XP 752, XP 755, P 750, P 3125 from DSM, Uvecoat (2100, 2200, 2300 from Allnex, Reafree UV (2130 and 2223 from Arkema and PUDRALAC 250 from Megara

The crosslinking agent comprised in the gel coat coating formulation of the present invention must contain one or more carbon-carbon double bonds and, preferably, this compound is solid at a temperature equal to or less than 25 ° C. It must be able to react under the conditions of cure temperature, preferably between 80 ° C and 150 ° C and with the help of an organic peroxide, with the unsaturated fragments of the

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unsaturated polyester resin. Possible families of crosslinking agents may be, for example, acrylates, methacrylates, esters and vinyl ethers, vinyl amides, itaconates, acrylamides, maleic anhydride and their copolymers and monomers with at least one allyl group.

Additionally, the coating formulation described in this patent application comprises a radical polymerization initiator, in particular, an organic peroxide. This compound will allow the thermosetting structure to be obtained, that is, the electrically conductive gel coat coating, by radical polymerization of the unsaturated polyester solid resin with the crosslinking agent, at a cure temperature between 110 and 150 ° C.

Different initiators have different decomposition rates depending on their structure and the radicals they produce. These differences can be adequately expressed in terms of the half-life (t1 / 2) of the initiator, where the half-life is defined as the time necessary for the concentration of the initiator to decrease to half of its original value at a given temperature. For example, t-butyl perbenzoate (commercially available as Luperox P) has a half-life of 1.0 hour at 125 ° C, 1.0 min at 171 ° C and 1 second at 228 ° C.

The peroxides that can be used comprise the following families, diacyl peroxide, dialkyl peroxydicarbonate, tert-alkyl peroxiester, di- (tert-alkyl) peroxystal, di-tert-alkyl peroxide. Additionally, mixtures of various initiators such as those mentioned above may also be used in the present invention.

In some preferred embodiments of the present invention, the gel coat powder coating formulation of the present invention comprises inhibitors, in particular, benzoquinones or hydroquinones such as, for example, hydroquinone (HQ), toluhydroquinone (THQ), mono-tert- butylhydroquinine (MTBHQ) or 2,5-di-tert-butylhydroquinione (BTBHQ). Preferably, these inhibitors are present in concentrations between 50 and 100 ppm. These inhibitors help control the shelf life and gelation time of the formulation.

On the other hand, the gel coat powder coating formulation of the present invention may comprise accelerators or promoters to regulate the properties of gelation and

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gel coat curing. Examples of these accelerators may be cobalt stearate, cobalt acetylacetonate or cobalt neodecanoate.

In particular embodiments, the present invention relates to the gel coat powder coating formulation where the conductive carbon particles are incorporated into the unsaturated polyester resin, and these particles are present in an amount between 0.5% and 70% by weight regarding the weight of the formulation. Preferably, the carbonaceous particles are present in an amount sufficient to give rise to a gel coat coating with an electrical conductivity between 1 to 10-12 S / cm.

The carbon particles present in the gel coat formulation of the present invention may be carbon nanotubes, carbon black, graphite, graphene, carbon fibers or a combination of the foregoing.

In preferred embodiments, the carbonaceous particles have a particle size between 1 nm and 4 mm, both limits included.

Carbon nanotubes are tubular structures whose diameter is generally of the order of the nanometer. Its structure can be considered as coming from a sheet of graphite rolled on itself. Depending on the degree of winding and the way the original sheet is formed, the result can lead to nanotubes of different diameter and internal geometry. Shaped nanotubes as if the corners of a folio were joined at their ends forming a hairpin, are called monolayer nanotubes, or SWNTs (Single-Walled Nanotubes). There are also nanotubes whose structure resembles that of a series of concentric tubes, included inside each other as "matriuska dolls" and logically of increasing thicknesses from the center to the periphery. The latter are multilayer nanotubes or MWNTs (Multi-walled Nanotubes). Derivatives are known in which the tube is closed by half a fullerene sphere, and others that are not closed. The present invention preferably comprises double-walled nanotubes. Preferably, the conductive gel coat formulation comprises between 0.5% by weight to 20% by weight, but more preferably from 0.5% by weight to 10% by weight of carbon nanotubes, amounts expressed in% by weight with respect to to the total weight of the formulation.

Graphene consists of a sheet of very fine carbons (they are the size of an atom), and hexagonal cells. Graphene is usually obtained from graphite and can

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presented in the form of foil and dust. Its origin can be natural or synthetic. Preferably, the conductive gel coat formulation comprises reduced graphene oxides (RGO) in an amount ranging from 0.5% by weight to 60% by weight, more preferably from 2% by weight to 40% by weight, amounts expressed in% in weight with respect to the total weight of the formulation.

Carbon black is an additive used in polymers such as pigment or conductive additive. The selection of the appropriate carbon black is very important to obtain conductive compounds. The key properties are particle size, structure and purity. Examples of carbon blacks that can be used in the formulation in the present invention comprise superconducting carbon blacks with high aspect ratio. Preferably, the coating formulation of the invention comprises between 1% by weight to 70% by weight, more preferably between 1% to 50% by weight, of carbon blacks, amounts expressed in% by weight with respect to the total weight of the formulation .

Graphite is one of the three main allotropic forms of carbon. Its structure is characterized by having carbon rings organized in parallel planes. The properties of graphite are determined mainly by electrical and thermal conductivity, lubricating properties, high resistance to thermal stress, resistance to oxidation and chemical agents. Preferably, the coating formulation of the invention comprises graphite percentages of 1% to 70% by weight and, more preferably, 1% to 50% by weight, amounts expressed in% by weight with respect to the total weight of the formulation.

Additionally, the gel coat powder coating formulation described in this patent application may comprise compounds to improve the dispersion of fillers in the resin, improve the processability or applicability of the coating, fillers or other additional ingredients that provide it specific properties such as, for example, greater color stability, ease of handling, speed of curing, compatibility with other resins, ease of maintenance and greater elongation. To allow these variants, the formulation may comprise additional ingredients such as pigments, fillers, accelerators, or inhibitors to extend the half-life.

The incorporation of fillers in the formulation allows to achieve certain desired characteristics and alter the aerosol properties. Water and other factors

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Environmental effects can affect the color, texture or appearance of the gel coat. Filling materials can modify the physical properties of the formulation, making it more resistant to these conditions. Fillers are widely used in powder coating formulations to modify functional properties such as hardness; module; permeability; corrosion, abrasion, chipping resistance; brightness; texture; inflammability; and electrical characteristics. Most fillers are inorganic and usually are in their fully oxidized state. These compounds are usually heat stable, resistant to ultraviolet degradation and chemical attacks, and do not interact with the binding system.

In preferred embodiments, the gel coat coating formulation of the present invention comprises an inert filler material that has one or more of the following characteristics: does not interact with the binder system, resistant to light and does not fade, resistant to solvents, acids and bases, chemical and mordant products, heat stable, insoluble in water and organic solvents, properties such as constant composition, particle size and distribution, low density, non-toxic, non-harmful, non-abrasive and economical.

Fillers that may be comprised in the formulation of the present invention may be, for example: calcium carbonate, talc, aluminum trihydrate, barium sulfate, wollastonite, nepheline sienite, kaolin, leukophilite, lithopon, cristobalite, silica, alumina, feldspar , hollow glass microspheres, glass microspheres, hollow ceramic microspheres.

On the other hand, additives are used to modify the specific properties of the gel coat coating formulation. In particular, these compounds can be used, for example, to increase durability, improve processability, improve final appearance and prevent defect formation.

In preferred embodiments of the present invention, the gel coat coating formulation of the present invention comprises at least one additive selected from the group consisting of additives to control fluidity, additives to modify appearance, additives to improve external durability, antistatic agents or load control, agents for controlling brightness, texturizing additives, additives for controlling slippage and surface deterioration and post-mixing additives.

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The present patent application also refers to a process for obtaining the solid gel coat or gel coat type formulation, with electrically conductive properties described in this patent application, where the process can be carried out in a Conventional extrusion machine such as, for example, a co-rotary or counter-rotary twin screw extruder.

In preferred embodiments, the process of obtaining the solid and electrically conductive gel coat coating formulation of the present invention comprises:

- add the following ingredients separately or together to an extrusion equipment:

i) solid unsaturated polyester resin;

ia) optionally, additional additives other than those mentioned in i), ii) and iii);

ii) particles of one or more carbonaceous conductive materials; Y

iii) crosslinking agent and organic peroxide; Y

- Extrude at a molding temperature between 20 ° C and 130 ° C, preferably between 40 ° C and 100 ° C.

Additionally, when the gel coat formulation of the invention comprises at least one additional ingredient such as, for example, fillers, pigments, accelerators, inhibitors, helpers in the extrusion process, etc., these can be incorporated mixed with any of the ingredients essentials mentioned above, in particular together with the unsaturated polyester solid resin, carbonaceous particles or the mixture of crosslinking agent and organic peroxide. Alternatively, they can also be incorporated into the extrusion mixture separately from the rest of the ingredients.

Alternatively, the present invention also relates to a process for obtaining the gel coat coating formulation described in this patent application, characterized in that the process comprises:

- add the coating ingredients together to an extrusion equipment, and

- Extrude at a molding temperature between 20-130 ° C, preferably between 40 and 100 ° C.

Advantageously, the gel coat coating formulation of the present invention can be obtained in conventional extrusion equipment such as, for example, a co-rotating and counter-rotating double screw extruder with different L / D ratios (length / diameter) between 15 and 56, preferably between 20 and 40.

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Additionally, the process of obtaining the solid and conductive gel coat coating formulation described in this patent application may comprise a lamination step of the extrudate.

The process described in this patent application may also comprise one or more stages of grinding, sieving, micronizing or combination of the foregoing in order to obtain a solid coating formulation with the desired particle size, preferably, a particle size between 0 and 150 microns.

Another aspect of the present invention relates to the use of the gel coat coating formulation described in this patent application to obtain a thermoset electrically conductive coating, where the process of obtaining the coating takes place at a curing temperature between 110-150 ° C. Preferably, the curing process that results in the coating takes place between 1 and 30 minutes.

In particular embodiments of the present invention, the gel coat coating formulation is polymerized on a mold at a temperature between 100 and 150 ° C. In the present invention this polymerization temperature can be achieved by heated molds (internal electrical or liquid circuits) or by applying different types of radiation thereon which can comprise thermal radiation, infrared radiation, microwave radiation, or ultraviolet radiation. In these cases, it is preferred that the mold has been previously treated with a mold release material, to thereby facilitate the demolding process of the gel coat obtained. Additionally, in these cases it is advisable to pay special attention to the mold, since any dirt or defect on its surface (eg scratches, dents or wear) can affect the molded gel coat obtained. The release agents comprising the present invention may be water based or solvent based.

Additionally, the present invention relates to the electrically conductive gel coat coating obtained from the coating formulation defined in this application. As well as the composite material comprising said electrically conductive coating.

In preferred embodiments, this electrically conductive coating has an electrical conductivity greater than the electrical conductivity of a coating obtained in

the same conditions from a formulation equal to that used, but without comprising carbonaceous particles. Preferably, the gel coat coating of the present invention has an electrical conductivity between 1 and 10-12 S / cm.

5 BRIEF DESCRIPTION OF THE FIGURES

Figure 1: Graph of electrical conductivity data obtained for the gel coat coating with electrical conductivity properties using different amounts of carbon black.

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Figure 2: Graph of electrical conductivity data obtained for the gel coat coating with electrical conductivity properties using different amounts of carbon nanotubes.

15 EXAMPLES

The following are some non-limiting examples of gel coat base formulations used to obtain the powder gel coat coating formulation with electrical conductivity properties of the present invention by adding different percentages of carbonaceous fillers:

Example 1: Obtaining a gel coat powder formulation with electrical conductivity properties using carbon black.

 Composition (parts by weight)

 Unsaturated polyester

 61.00

 Trialyl isocyanurate (TAIC 70)

 2.60

 Di- (4-t-Butyl cyclohexyl) peroxydicarbonate (Peroxan BCC)

 1.30

 Carbon black

 13.00

 Film training improvement

 18.22

 Abrasion Improvement

 0.20

 Process aids:

 Internal release agent

 1.33

 Viscosity modifier

 2.35

 Total

 100.00

The electrical conductivity results shown in Figure 1 correspond to different formulations of composition similar to that indicated above, where the amount of carbon black has been modified.

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Example 2: Obtaining the gel coat powder coating formulation with electrical conductivity properties using carbon nanotubes.

 Composition (parts by weight)

 Unsaturated polyester

 70.00

 Trialyl isocyanurate (TAIC 70)

 2.00

 Di- (4-t-Butyl cyclohexyl) peroxydicarbonate (Peroxan BCC)

 0.80

 Carbon nanotube

 3.00

 Film training improvement

 20.00

 Improves abrasion

 0.20

 Process aids

 Internal release agent

 1.00

 Viscosity modifier

 3.00

 Total

 100.00

10 The electrical conductivity results shown in Figure 2 correspond to different formulations of composition similar to that indicated above, where the amount of carbon nanotubes has been modified.

Claims (16)

5 10 fifteen twenty 25 30 1. - A gel coat powder coating formulation with electrical conductivity properties, characterized in that it comprises: a solid unsaturated polyester resin, a crosslinking agent comprising at least one carbon-carbon double bond, an organic peroxide polymerization initiator, and electrically conductive carbon particles. 2. - Coating formulation according to claim 1, in the form of micronized powder. 3. - Coating formulation according to any one of claims 1 to 2, wherein the dust particles have a particle size between 1 to 100 microns. 4. - Coating formulation according to any one of claims 1 to 3, wherein the carbonaceous particles are incorporated into the unsaturated polyester resin, and are present in an amount between 0.5% and 70% by weight with respect to the weight of the formulation. 5. - Coating formulation according to any one of claims 1 to 4, wherein the carbonaceous particles are selected from the group consisting of carbon nanotubes, carbon black, graphite, graphene, carbon fibers and a combination of the above. . 6. - Coating formulation according to any one of claims 1 to 5, wherein the carbonaceous particles have particle size ranges from 1 nm to 4 mm. 7. - Coating formulation according to any one of claims 1 to 6, wherein the crosslinking agent is selected from the group consisting of acrylates, methacrylates, esters and vinyl ethers, vinyl amides, itaconates, acrylamides, maleic anhydride and its copolymers and monomers with at least one allyl group. 8. - Coating formulation according to any one of claims 1 to 7, wherein the organic peroxide is selected from the group consisting of diacyl peroxide, 5 10 fifteen twenty 25 30 35 dialkyl peroxydicarbonate, tert-alkyl peroxiester, di- (tert alkyl) peroxyacetal, di-tert-alkyl peroxide and any combination of the foregoing. 9. - Coating formulation according to any one of claims 1 to 8, comprising at least one additional ingredient selected from the group consisting of compounds to improve the dispersion of the charges in the resin, improve the processability or applicability of the coating, material of filler, pigments, accelerators, inhibitors and a combination of the above. 10. - Process for obtaining the coating formulation described in any one of claims 1 to 9, characterized in that the process comprises: - add the following ingredients separately to an extrusion equipment: i) solid unsaturated polyester resin; ii) particles of one or more carbonaceous conductive materials; Y iii) crosslinking agent and organic peroxide; Y - Extrude at a molding temperature between 20 ° C and 130 ° C. 11. - A process for obtaining the coating formulation defined in any one of claims 1 to 9, characterized in that the process comprises: - add the coating ingredients together to an extrusion equipment, and - Extrude at a molding temperature between 20 ° C and 130 ° C. 12. - The process according to any one of claims 10 and 11, comprising an additional stage of lamination of the formulation obtained by extrusion. 13. - The process according to any one of claims 10 to 12, comprising an additional stage of grinding, sieving, micronization or a combination of the foregoing. 14. - Use of the coating formulation described in any one of claims 1 to 9 to obtain a thermoset electrically conductive coating, where the process of obtaining the coating takes place at a curing temperature between 110 ° C and 150 ° C 15. - Use of the coating formulation according to claim 14, wherein the curing process takes place between 1 and 30 minutes. 16. An electrically conductive coating obtained to defined in any one of claims 1 to 9. 17. The coating according to claim 16, wherein the electrical conductivity superior to the coating obtained from but not including carbonaceous particles. starting from the formulation coating has one of the same formulation,