MX2008009093A - Process for manufacturing particles based on natural calcium carbonate and salts of acrylic acid-ethylene, suspensions and dry pigments obtained, and uses thereof - Google Patents

Abstract

The present invention consists in a process for preparing at least one mineral material and/or at least one pigment, comprising a calcium carbonate made both partially organophilic and partially hydrophilic, wherein the carbonate is mixed and/or ground and/or concentrated in aqueous medium in the presence of at least one salt of ethylene acrylic acid, a dispersant and/or grinding aid being introduced before and/or during this treatment step. Another subject of the invention lies in the resulting dispersions and aqueous suspensions of calcium carbonate. They may be dried, and the dry pigments obtained likewise constitute a subject of the invention. The useof these aqueous dispersions and of these dry pigments in the field of plastics, paints and paper constitutes another subject of the invention.

Description

PROCESS FOR MANUFACTURING PARTICLES BASED ON NATURAL CALCIUM CARBONATE AND ACRYLIC ETHYLENE ACID SALTS, SUSPENSIONS AND DRY PIGMENTS OBTAINED AND THEIR UTILIZATIONS DESCRIPTION OF THE INVENTION A first object of the present invention consists in a process for the preparation of at least one mineral material and / or of at least one pigment, which includes a natural calcium carbonate and / or a precipitate, preferably natural, made to the partially organophilic and partially hydrophilic, and which includes the following steps: a) supplying at least one mineral material and / or at least one pigment containing natural calcium carbonate and / or precipitate, in dry form or in the form of a dispersion and / or of an aqueous suspension, b) optionally milling in dry and / or aqueous medium the mineral matter and / or the pigment resulting from stage a), c) treating the mineral matter and / or pigment resulting from step a ) and / or step b), d) optionally drying the mineral matter and / or pigment resulting from step a) and / or b) and / or c), characterized in that: - step c) of treatment corresponds to a stage of mixing in aqueous medium and / or grinding Re f .: 194660 in aqueous medium, and / or concentration in aqueous medium, of the mineral material and / or pigment from stage a) and / or stage b), in the presence of at least one salt of ethylene acrylic acid, a Dispersing and / or grinding aid agent is introduced before and / or during the treatment step c). A second object of the present invention lies in the suspensions and aqueous dispersions obtained by said process. A third object of the present invention lies in the dry products obtained by said process. A fourth object of the present invention resides in the use of aqueous suspensions and dispersions and of dry products in the manufacture of plastics, paints and papers, and in particular in plastic or paper coating, as well as in the plastic mass load or paper basket. The main objective of the process is the treatment and / or economic production of a mineral material and / or a pigment that includes a natural calcium carbonate and / or precipitate. In particular, the process of the invention allows the expert to obtain a dispersion of mineral matter and / or pigment treated in this way with a high solids content (expression that will be retaken throughout the present Application, and defined as the percentage by dry weight of mineral matter and / or pigment with respect to the total weight of the dispersion). A high solids content, and in particular higher than 65%, preferably 70%, very preferably higher than 75% of the total weight of the dispersion leads to a decrease in the transport costs of the dispersion, and a decrease in costs of drying the dispersion. The process according to the invention makes it possible in particular to obtain the solids contents, while maintaining the dispersion advantageous rheological properties, the dispersion being still easily manipulated, which avoids the significant presence of agglomerates. A second objective is to provide the skilled person with the possibility of treating the mineral matter and / or the pigment containing a natural calcium carbonate and / or precipitate to be both partially organophilic and partially hydrophilic, both during a grinding step, and during a mixing step, such as during a concentration stage, which are the stages usually developed during the overall process of manufacturing an aqueous dispersion of mineral matter; These different possibilities offer flexibility to the expert.

A calcium carbonate made in this way organophilic can be advantageously used in the field of plastics: on the other hand, hydrophilic character will allow dispersing it at high concentrations in water, that is to say obtaining aqueous dispersions or suspensions of calcium carbonate whose content by weight dry matter of minerals - will in particular be greater than 65% of total weight, maintaining at the same time advantageous rheological properties and without the formation of agglomerates. In plastic materials, such as in particular thermoplastic resins or thermosetting resins, mineral materials and / or pigments are usually incorporated, such as, for example, natural or precipitated calcium carbonate, dolomites, magnesium hydroxide, kaolin, talc, gypsum, or even titanium oxide. These mineral materials and / or pigments can improve particular properties of these plastic materials, as in the case of the use of calcium carbonate in PVC, the increase in stiffness, the improvement of thermal exchanges during extrusion, or even the reduction of the deposit at the departure of filiar. For this, the Applicant may mention the document "The use of calcium carbonate to enhance the physical properties of rigid vinyl products" (Society of Plastic Engineers, Conf., 12-14 October 1999). On the other hand, it is also usual replace a part of the plastic resins, expensive materials, by these pigments and / or mineral materials. In the framework of the use of calcium carbonate in plastic materials, the expert manufacturer of mineral materials in particular with a view to their use in plastic materials knows that in order to improve the compatibility of carbonate with the plastic material in which it is incorporated, it is necessary treat calcium carbonate. For this reason, it has been known for many years, the use of fatty acid derivatives as treatment agents of calcium carbonate, including these fatty acids in particular of 10 to 20 carbon atoms, and more particularly of 16 to 18 carbon atoms in a saturated carbon structure (such as stearic acid), palmitic and / or stearic acid and its salts being the agent or agents preferably used by the skilled artisan. It is important to indicate that calcium carbonate is prepared according to various stages of manufacture in aqueous medium, such as dispersion, grinding or even concentration stages. The product resulting from these steps is a dispersion or an aqueous suspension of calcium carbonate, which optionally contains different dispersing and / or aid agents for grinding and / or treatment introduced during these various stages. In general, by adding stearic acid (or in the molten state, or in the form of an emulsion) in a dispersion or suspension of calcium carbonate, or dry calcium carbonate, an additional stage of disaggregation must be carried out after this incorporation. In case of using an emulsion of stearic acid, where an emulsifier can be introduced in order to stabilize this emulsion, the presence of the emulsifier can cause destabilization of the dispersion or suspension of calcium carbonate, which is translated by the formation of flocculated particles and / or particles on the surface. This emulsifier has the additional drawback of inducing the creation of foam in the dispersion or suspension. This shows a first drawback related to the use of stearic acid: it requires the incorporation of additional stages and / or additives, sometimes with negative consequences during the treatment process. The selection of treatment carried out with salts of stearic acid, as neutralized with calcium ions, also does not lead to the solution sought by the expert: it also has the drawback of inducing the creation of foam in the dispersion or suspension of calcium carbonate. Finally, it appears that the use of stearic acid or its salts does not make it possible to obtain aqueous suspensions or dispersions of calcium carbonate with a concentration by weight of dry mineral matter exceeding 65% of the total weight of the dispersion or suspension with an exploitable viscosity and / or without the creation of agglomerates leading to the presence of recovered residues on the filtration screens. However, calcium carbonate is usually manufactured according to the steps described above, transported in the form of dispersion or aqueous suspension, optionally stored under this same form, and finally dried before being incorporated into the plastic material, for economic reasons, it is essential for the expert to manufacture and supply to the final transformer a dispersion or an aqueous suspension of calcium carbonate having a solids content as high as possible, maintaining a satisfactory viscosity and / or without the significant creation of agglomerates and therefore of waste recovered on sieves, which does not allow the use of stearic acid or its salts. To solve these different problems related to the use of stearic acid or its salts, in order to treat a mineral matter to be both partially organophilic and partially hydrophilic (and in particular calcium carbonate) with a view to its incorporation in the plastics and to manufacture it economically, the Applicant has developed a new process for the preparation of at least one mineral material and / or at least one pigment that includes natural calcium carbonate and / or precipitate which is both partially organophilic and partially hydrophilic, and which includes the following steps: a) supplying at least one mineral material and / or a pigment containing natural calcium carbonate and / or precipitate, in dry or of a dispersion and / or of an aqueous suspension, b) optionally grinding in dry and / or in aqueous medium the mineral matter and / or the pigment resulting from stage a), c) treating the mineral matter and / or the pigment resulting from step a) and / or step b), d) optionally drying the mineral matter and / or the pigment resulting from step a) and / or b) and / or c), characterized in that: - stage c ) of treatment corresponds to a stage of mixing in aqueous medium and / or grinding in an aqueous medium, and / or concentration in an aqueous medium, the mineral matter and / or the pigment from stage a) and / or step b), in the presence of at least one salt of ethylene acrylic acid, - a dispersing agent and / or aid to the mold is introduced before and / or during the treatment step c).

Said process therefore makes it possible, very surprisingly, to incorporate the treatment agent in order to manufacture suspensions of natural calcium carbonate and / or precipitate of solids contents higher than those obtained by the prior art processes using stearic acid or its salts, while maintaining a satisfactory viscosity and / or without the significant creation of agglomerates and therefore of residues recovered on screens, and without the drawbacks of this prior art. It is especially very surprising that, inasmuch as the ethylene acrylic acid salts are added during or after adding dispersant, the salts do not adversely affect the rheological properties of the dispersions obtained: indeed, they are achieved in a surprising manner , according to the process of the invention, contained in high solids (and in particular higher than 65%) with good rheological properties and without the formation of agglomerates. In parallel, it is very surprising that the dispersant (which is added before or during the introduction of the ethylene acrylic acid salts), does not impede the interaction between the salts and the surface of the calcium carbonate in order to make it organophilic; in fact, it is achieved surprisingly, with the process according to the invention, to manufacture calcium carbonate particles dispersible in plastic materials.

The Applicant wishes to indicate that there is a certain number of documents that relate the use of ethylene acrylic acid in a manufacturing process of calcium carbonate.

Referring to this issue, he wishes to underline: - First, that none of these documents seeks to solve the same technical problem as that of the present Application, - on the other hand, that none of these documents reveals the technical solution of the present Application that it consists of the process described above, moreover, that nothing suggests in one of these documents, or in the possible combinations of one or several of these documents between them or with other documents, the process according to the invention; and on the contrary, the teaching of these documents could not lead the expert to the process object of the present invention. These arguments will be developed below, with respect to the content and teaching revealed by each of the documents related to the use of ethylene acrylic acid during a manufacturing process of calcium carbonate. The expert knows US Patent No. US 6 808 809 which seeks to solve the technical problem of manufacturing a mineral filler having in particular a good castability; for this, this document does not solve the same technical problem as the object of the present Application. The proposed solution consists of introducing into a dryer an aqueous suspension of mineral filler (such as calcium carbonate) with an average diameter of less than 15 μm, and an aqueous polymer dispersion (such as, in particular, ethylene acrylic acid). ). This document indicates that the mineral charge suspension may have a solids content included between 10% and 90% of the total weight of the suspension; however, only example 1 performed in the case of aluminum trihydroxide reveals a solids content value, which is equal to only 55%. On the other hand, nothing is indicated about the viscosity of the suspensions obtained, nor about the possibility of reducing the amount of agglomerates of mineral matters. The Applicant emphasizes that in no case does this document disclose the use of ethylene acrylic acid in the form of salts, which therefore constitutes an element of distinction with the present invention. Finally, there is nothing to suggest to the expert that the use of a dispersing agent be particularly important in this document, and a fortiori the use of a dispersing agent before the use of ethylene acrylic acid in the form of salts; likewise, nothing in this document suggests-focused on a drying process-a process according to the invention that offers the possibility of treating a calcium carbonate both during a grinding step, as a mixture or a concentration step and this, in the presence of at least one salt of ethylene acrylic acid, and of a dispersing or grinding aid used before the treatment step of the calcium carbonate. The expert also knows the publication WO 93/11183 which seeks to solve the technical problem to improve the dispersion of inorganic particles in different materials, such as paints, adhesives, mastics, or even binders for non-woven materials; it is therefore a technical problem different from that solved by the present Application, since it does not deal in particular with the issue of manufacturing suspensions in a process for the preparation of a stable aqueous dispersion, by mixing an aqueous suspension of inorganic particles ( such as calcium carbonate) and an aqueous suspension of latex polymer particles, after having adjusted their zeta potentials. The ethylene acrylic acid is described as one of the polymers that can be used, without ever being exemplified or without being distinguished in particular among all the usable polymers. On the other hand, the examples show that the resulting suspensions have low solids contents, and always lower than 60% by dry weight of mineral particles with respect to the total weight of the suspensions. An element of A fundamental difference with the present invention is that this document never indicates the presence of ethylene acrylic acid salts. Finally, there is nothing to suggest to the expert that the use of a dispersing agent be particularly important in this document, and a fortiori the use of a dispersing agent before the use of ethylene acrylic acid in the form of salts; likewise, nothing suggests in this document - focused on a mixing process - a process according to the invention that offers the possibility of treating a calcium carbonate both during a grinding step, as a mixture or as a concentration step and this, in the presence of the less a salt of the ethylene acrylic acid, and of a dispersing agent or aid to the milling used before the treatment step of the calcium carbonate. The expert also knows the publication WO 97/13815 which seeks to solve the technical problem of making powders compatible with plastics (but also paints, paper), to avoid the coalescence of the particles that constitute the powders, to make the surface of hydrophobic calcium carbonate; for this, this document only partially solves the problem object of the present Request. In fact, the solution proposed does not allow aqueous suspensions of calcium carbonate with a solids content higher than 6% with respect to the total weight of the suspensions to be obtained, as shown in particular by the results in Table 2. In addition, the solution proposal it consists in dissolving at first a polymer (such as ethylene acrylic acid) in a medium containing a carboxylic acid, and then in contacting the product obtained with the calcium carbonate in order to precipitate it on it: This stage of dissolution constitutes an element of fundamental differentiation with the present invention. Furthermore, this dissolution step, when long chain carboxylic acids are used, will lead to the same problems as those resulting from the use of stearic acid, that is to say in the need of an additional stage of deagglomeration and / or incorporation of additives. additional calcium carbonate particles. This same dissolution stage, when using shorter chain carboxylic acids, will lead to the inoculation of the calcium carbonate particles and will therefore not allow to obtain aqueous suspensions with a high solids content and in particular higher than 65% of the total weight of suspensions. These shorter chain carboxylic acids can also destroy the calcium carbonate particles, and even generate carbon dioxide. Finally, these short chain carboxylic acids can reduce the resistivity and increase the conductivity of the plastics materials in which the calcium carbonates according to the invention are finally used. Finally, nothing suggests to the expert to give particular importance to the use of a dispersing agent in this document, and a fortiori the use of a dispersing agent before the use of ethylene acrylic acid in the form of salts; likewise, nothing suggests in this document - focused on a mixing process - a process according to the invention that offers the possibility of treating a calcium carbonate both during a grinding step, as a mixture or as a concentration step and this, in the presence of the less a salt of the ethylene acrylic acid, and of a dispersing agent or aid to the milling used before the treatment step of the calcium carbonate. The expert also knows the publication WO 02/96982 which seeks to solve the technical problem of manufacturing an inorganic organic nanocomposite material, while reinforcing inside the material the compatibility between organic particles and inorganic particles; for this, this document does not solve the same technical problem as the object of this Application. The proposed solution consists of forming a mixture between a mineral particle (such as calcium carbonate) and a polymer solution (such as, for example, based on ethylene acrylic acid) in the presence of solvents, in evaporating the solvents, and in mixing the product obtained with a polymer resin. This document does not provide any indication on the solids contents of the mineral particle and polymer mixtures. On the other hand, it has the disadvantage of using solvents (as in particular THF and ethanol) whose presence is undesirable for the expert, in particular because they will emit a significant percentage of volatile organic carbon (VOC) into the atmosphere. Finally, this process is different from the object of the present invention, since it does not indicate the presence of dispersing agent. Finally, nothing in this document suggests-focused on a mixing process-a process according to the invention that offers the possibility of treating a calcium carbonate during a grinding, mixing or concentration stage and in the presence of at least one salt of the ethylene acrylic acid, and of a dispersing agent or of a grinding aid used before the treatment step of calcium carbonate. The expert also knows US Pat. No. 5,439,402 which seeks to solve the technical problem of irreversibly binding a mineral filler and an organic modifier, which then enters into the composition of aqueous coatings whose opacity and gloss are improved; for this, this document does not solve the same technical problem as the object of the present Application. The proposed solution is to make a pigment from calcium carbonate particles in the flocculated state and an anionic modifying agent (such as polymers and in particular ethylene acrylic acid), then calcium carbonate and the modifying agent are linked one to another by electrostatic bonds. The general teaching of this document is that, in order to treat a calcium carbonate in particular with a solution of ethylene acrylic acid, it is preferable to initially have a pigment in flocculated form (column 4, lines 39 to 62) and not of a dispersed pigment (as explicitly stated in line 50 of column 4), this dispersed state being defined as resulting from the incorporation of an agent that has led to a decrease in viscosity or to a reduction in the size of the particles (column 1, lines 15 to 25). A dispersing agent such as a sodium polyacrylate can then be added after the introduction of the ethylene acrylic acid solution (column 4, lines 63 to 65). Accordingly, the skilled person is strongly encouraged not to use dispersant before the treatment of calcium carbonate with a solution of ethylene acrylic acid. This dispersed state, as defined in U.S. Patent No. US 5 449 402 as a result of the incorporation of an agent that leads to a decrease in viscosity or a reduction in the size of the particles, is therefore undesirable in this document; however, it forms part of one of the fundamental characteristics of the present invention. Indeed, the Applicant has been able to observe that, in a surprising way since very contrary to previous art teaching, the introduction of a dispersing agent It is mandatory before or during the incorporation of salts of acrylic ethylene acid to treat calcium carbonate, thus making calcium carbonate both partially organophilic and partially hydrophilic, without using stearic acid, allowing to obtain aqueous suspensions with a solids content high and good rheology and without agglomerates, and allows to provide the expert with a very flexible process since ethylene acrylic acid can be used during a stage of grinding, mixing, or concentration. Nor does any of the documents accessible to the expert on the use of ethylene acrylic acid correspond to the same technical problem as that solved by the present Application. Likewise, none of them discloses the technical solution object of the present Application. Finally, none of them, nor their combinations among them or with other documents, suggests the technical solution object of the present Application. One of the merits of the Applicant lies in particular in the fact that it has been noted that the following particular decisions: - the use of ethylene acrylic acid salts to treat a natural calcium carbonate and / or precipitate, - the incorporation of a dispersing agent and / or aid to grinding before and / or during the treatment step of calcium carbonate by the salts of ethylene acrylic acid (which is contrary to the teaching of the state of the art), they allow in a surprising way the set-up of a process: - that avoids the inconveniences related to the use of stearic acid (stage of deagglomeration and incorporation of additional additives), which represents a financial saving, which allows to obtain aqueous suspensions of materials minerals with a high solids content (in particular higher than 65%) with a good rheology and without the presence of agglomerates that would create residues on the filtration sieves, which represents a technical and economic interest, which allows the expert to be provided with a process where you can treat calcium carbonate during a grinding stage, as well as mixing or concentrating in an aqueous medium, which represents a very great flexibility. In addition, this process makes it possible to obtain a natural calcium carbonate and / or precipitate at the same time partially organophilic and partially hydrophilic, which is very surprising. It is particularly surprising that, in so far as the ethylene acrylic acid salts are added during or after adding dispersant, the salts do not adversely affect the rheological properties of the dispersions obtained: in fact, they are surprisingly achieved , according to the process of the invention, contained in high solids (and in particular higher than 65%) with good rheological properties and without the formation of agglomerates. In parallel, it is very surprising that the dispersant (which is added before or during the introduction of the ethylene acrylic acid salts), does not prevent the interaction between the salts and the surface of the calcium carbonate in order to make it organophilic: in fact, Surprisingly, with the process according to the invention, it is possible to produce dispersible calcium carbonate particles in plastics. Finally, the Applicant wishes to indicate that it is aware of French Patent Application No. 04 07806 registered but not yet published, and that therefore it intervenes only as a novelty in order to evaluate the patentability of this Application. French Patent Application No. 04 07806 describes a process for the preparation of pigment particles that are self-ligating, dry or in suspension or dispersion aqueous, which includes the following steps: a) forming one or more aqueous suspensions of at least one inorganic material and introducing it (s) in a mill with a view to step c), b) forming or taking one or more solutions or suspensions or Aqueous emulsions of at least one binder and introducing it (s) in a mill with a view to step c)c) compacting the aqueous suspension (s) obtained in step a) with the aqueous solutions or suspensions or emulsions obtained in step b) in order to obtain an aqueous suspension of self-ligating pigmentary particles, d) optionally suspending the suspension aqueous obtained in step c) with one or several solutions? aqueous suspensions or emulsions of at least one binder, e) optionally drying the aqueous suspension obtained in step c) or in step d). This process, as indicated in the French Patent Application No. 04 07806, prevents the expert from resorting to a third component during the preparation of the aqueous suspensions containing the inorganic materials and the binders, as well as during the comolienda stage : this is therefore a fundamental difference with the present invention which necessarily involves a dispersing agent and / or a milling aid before or during the step of treating the mineral material with ethylene acrylic acid. Also, a first object of the invention lies in a process for the preparation of at least one mineral material and / or at least one pigment that includes natural calcium carbonate and / or a precipitate, preferably natural, at the same time partially organophilic and partially hydrophilic , and which includes the steps of: a) supplying at least one mineral material and / or a pigment that includes natural calcium carbonate and / or precipitate, preferably natural, in dry form or in the form of a dispersion and 7 or a suspension aqueous, b) optionally grind the mineral material and / or the pigment resulting from stage a), c) treat the mineral matter and / or the pigment resulting from step a) and / or from step b), d) optionally drying the mineral matter and / or the pigment resulting from step a) and / or b) and / or c), characterized in that: - the processing step c) corresponds to a mixing stage in the medium watery and / or grinding in an aqueous medium, and / or concentrating in an aqueous medium, the mineral material and / or the pigment from step a) and / or from step b), in the presence of at least one salt of ethylene acrylic acid, A dispersing agent and / or grinding aid is introduced before and / or during the treatment step c). The Applicant recalls that, according to this process, the mineral matter and / or the pigment which includes at least one natural calcium carbonate, when present in the form of a dispersion or an aqueous suspension, is not in the flocculated state as opposed to as claimed in U.S. Patent No. US 5 449 402. The process according to the invention is also characterized in that the salt of acrylic ethylene acid is a salt soluble in aqueous media. The process according to the invention is also characterized in that the carboxylic groups of the ethylene acrylic acid salt are partially or totally dissociated from its acid proton. The process according to the invention is also characterized in that, in the ethylene acrylic acid salt, the mass ratio of ethylene monomer to acrylic acid monomer is included between 10:90 and 30:70, and is preferably equal to :80. The process according to the invention is also characterized in that the salt of ethylene acrylic acid has a melt index included between 50 g / 10 minutes and 1,500 g / 10 minutes, preferably between 200 g / 10 minutes and 300 g / 10 minutes when the salt of ethylene acrylic acid is completely neutralized, and preferably between 1,000 g / 10 minutes and 1,400 g / 10 minutes when the salt of ethylene acrylic acid is neutralized from 70 to 99% (in fraction of carboxylic sites of ethylene acrylic acid), measured according to the ASTM1238 standard 125 ° C / 2.16kg. The process according to the invention is also characterized in that the carboxylic groups of the ethylene acrylic acid salts are completely neutralized or neutralized from 70 to 99% with respect to all the carboxylic sites of ethylene acrylic acid, with at least one neutralizing agent . The process according to the invention is also characterized in that said neutralizing agent includes at least one monovalent cation. The process according to the invention is also characterized in that said monovalent cation includes one or more alkali ions and / or one or more amines and / or ammonia. The process according to the invention is also characterized in that said alkali monovalent ion includes a sodium ion.

The process according to the invention is also characterized in that the amine includes a primary amine. The process according to the invention is also characterized in that the amine includes an alkanolamine, which includes at least one ethanol and / or propanol grouping, and wherein the alkanolamine is then preferably chosen from 2-amino-2-methyl-1-propanol and / or dimethylethanolamine, and in that 2-amino-2-methyl-1-propanol is most preferably. The process according to the invention is also characterized in that an amount of 2-amino-2-methyl-1-propanol is used, in order to provide a fraction of monovalent cation included between 75 and 125% of the carboxyl groups of the ethylene acrylic acid , and preferably in order to provide a monovalent cation fraction equal to 100% of the carboxylic groups of ethylene acrylic acid. The process according to the invention is also characterized in that an amount of dimethylethanolamine is used, in order to provide a monovalent cation fraction including between 75 and 125% of the carboxylic groups of ethylene acrylic acid, and preferably in order to provide a fraction of monovalent cation equal to 100% of the carboxylic groups of ethylene acrylic acid. The process according to the invention is also characterized in that said ethylene acrylic acid has a viscosity of 3,000 to 25,000 mPa.s, from 15,000 to 100,000 mPa.s, and 50,000 to 400,000 mPa.s at respective temperatures of 200 ° C, 170 ° C and 140 ° C. In a particular variant, the process according to the invention is characterized in that said ethylene acrylic acid has a viscosity of 3,000 to 7,000 mPa.s, of 15,000 to 20,000 mPa.s, and of 50,000 to 100,000 mPa. s at respective temperatures of 200 ° C, 170 ° C and 140 ° C. In another particular variant, the process according to the invention is characterized in that said acrylic ethylene acid has a viscosity of 15,000 to 25,000 mPa.s, of 50,000 to 100,000 mPa.s, and of 300,000 to 400,000 mPa. s at respective temperatures of 200 ° C, 170 ° C and 140 ° C. The process according to the invention is also characterized in that the mineral matter and / or the pigment includes, in addition to the calcium carbonate, also at least one other mineral material and / or pigment chosen from among the dolomites, bentonites, kaolin, talc, cement, gypsum, lime, magnesia, titanium dioxide, satin white, aluminum trioxide or even aluminum trihydroxide, silicas, mica and the mixture of these charges between them, such as talc calcium carbonate, calcium carbonate-kaolin, or even mixtures of calcium carbonate with aluminum trihydroxide or aluminum trioxide, or even mixtures with synthetic or natural fibers or even the co-structures of minerals such as talc- calcium carbonate or talc-titanium dioxide, or mixtures thereof, and in which this other mineral matter is preferably kaolin. The process according to the invention is also characterized in that the dry weight amount of calcium carbonate is greater than or equal to 70% of the total dry weight of pigments and / or mineral materials. The process according to the invention is also characterized in that, during stage a) and when the mineral matter and / or the pigment is present in the form of a dispersion and / or an aqueous suspension, the concentration in dry weight of pigment and / or mineral matter is greater than 60%, preferably 65%, most preferably greater than 70%, more preferably 74% to 78% of the total weight of the dispersion and / or suspension is included or, where the concentration in dry weight of pigment and / or mineral matter is less than 30%, preferably including between 18 and 22% of the total weight of the dispersion and / or suspension, and in that the dispersion and / or suspension is a suspension containing no dispersing agent. The Applicant emphasizes that these limitations affect stage a), and not the dispersion and / or aqueous suspension obtained after step c) for which it is sought to necessarily increase the solids content, which is part of one of the elements of the technical problem solved by the present Application.

The process according to the invention is also characterized in that the grinding stage b) is carried out continuously or discontinuously, preferably continuously. The process according to the invention is also characterized in that the grinding stage b) is carried out in the presence of grinding balls based on oxide and / or zirconium silicate, optionally stabilized with a cerium and / or yttrium oxide. In the variant according to which the grinding step b) is a dry grinding, the process according to the invention is also characterized in that this dry grinding step leads to the obtaining of mineral materials and / or pigments having a mean diameter less than 50 μm, preferably less than 15 μm, very preferably less than 5 μm, and even more preferably in which this average diameter is included between 1.3 and 1.7 μm, as measured from a Sedigraph ™ device 5100 marketed by the company MICROMERITICS ™. In the variant according to which the grinding step b) is a grinding in an aqueous medium, the process according to the invention is also characterized in that this grinding stage in an aqueous medium leads to the obtaining of mineral materials and / or pigments having a fraction of particles with a diameter of less than 2 μm greater than 60% (measured by a Sedigraph ™ 5100 device marketed by the company MICROMERITICS ™), or a fraction of particles smaller than 2 μm in diameter greater than 90% (measured by a apparatus Sedigraph ™ 5100 marketed by the company MICROMERITICS ™), or a fraction of particles with a diameter less than 2 μm greater than 99% (measured by a Sedigraph ™ 5100 device marketed by the company MICROMERITICS ™). The process according to the invention is also characterized in that the step c) of treatment leads to a dispersion and / or an aqueous suspension whose percentage by dry weight of mineral matters and / or pigments is greater than 65%, preferably greater than 70%, very preferably greater than 75%, and more preferably between 75 and 78% of the total weight of the dispersion and / or suspension. The process according to the invention is also characterized in that the step c) of treatment leads to a dispersion and / or an aqueous suspension whose mineral matters and / or the pigments have an average diameter of less than 50 μm, preferably less than 15 μm, very preferably less than 5 μm, and even more preferably in which this average diameter is included between 0.3 and 1.7 μm, and more preferably between 0.5 and 0.9 μm, measured by a Sedigraph ™ 5100 device marketed by the company MICROMERITICS ™ . The process according to the invention is also characterized in that the treatment step c) leads to a dispersion and / or an aqueous suspension having a particle fraction. with a diameter of less than 2 μm greater than 60% (measured by a Sedigraph ™ 5100 device marketed by the company MICROMERITICS ™), or a fraction of particles with an internal diameter 2 μm greater than 90% (measured by a Sedigraph device) "5100 marketed by the company ICROMERITICS ™), or a fraction of particles with a diameter less than 2 μm greater than 99-% (measured by a Sedigraph ™ 5100 device marketed by the company MICROMERITICS ™.) The process according to the invention is also characterized in that step c) of treatment leads to a dispersion and / or an aqueous suspension having a Brookfield ™ viscosity measured at 100 revolutions / minute (measured at 25 ° C, with the mobile n ° 3, and with the DVII + apparatus in a container of 1 liter) of less than 1,000 mPa.s, preferably less than 700 mPa.s, very preferably less than 500 mPa.s, and even more preferably in that this viscosity is included between 100 and 300 mPa.s. The proc This according to the invention is also characterized in that the treatment step c) leads to a dispersion and / or an aqueous suspension having a sieve residue greater than 45 μm, less than 100 ppm, preferably less than 70 ppm, more preferably less than 60 ppm, and more preferably less than 50 ppm. The process according to the invention is also characterized because step c) is preferably a step of grinding in an aqueous medium. The process according to the invention is also characterized in that the drying step d) is preferably carried out after step c) of treatment. The process according to the invention is also characterized in that the drying is carried out by an atomizing dryer. The process according to the invention is also characterized in that the dispersing and / or aid agent for grinding in an aqueous medium introduced during and / or before stage c) is a homopolymer of acrylic acid and / or a copolymer of acrylic acid with another water-soluble monomer chosen from methacrylic acid, maleic acid, itaconic acid, crotonic acid, fumaric acid, isocrotonic acid, aconitic, rnesaconic, sinapic, undecylenic, angelic, canonic and / or 2-acrylamido acid 2 methyl propanesulfonic in acid or partially neutralized form, or even between acrylamide, methylacrylamide, esters of acrylic or methacrylic acids such as, ethylene or propylene glycol acrylate or methacrylate phosphate or even between vinylpyrrolidone, vinylcaprolactam, acetate of vinyl, sodium styrene sulfonate, allylamine and its derivatives, and preferably in that the dispersing agent and / or aid to the grinding da is chosen from the copolymers of acrylic acid with acrylamide or maleic acid.

The process according to the invention is also characterized in that the dry milling agent used during grinding step b), when it is a dry grinding, is chosen from among glycol-based compounds, and preferably between ethylene glycol, diethylene glycol , the monopropylene glycol, and in that it is preferably a monopropylene glycol of molecular weight included between 200 and 1,000 g / mol. The process according to the invention is also characterized in that the total proportion of ethylene acrylic acid is included between 0.1 and 10%, preferably between 0.2 and 2%, and most preferably between 0.5 and 1% of the dry weight of pigments and / or mineral materials . The process according to the invention is also characterized in that the total proportion of dispersant and / or grinding aid agent is included between 0.1 and 2%, preferably between 0.2 and 1.5%, and is most preferably included between 0.3 and 0.6% by weight dry pigments and / or mineral materials. The process according to the invention is also characterized in that the amount by weight of acrylic ethylene acid is approximately equal to the amount by weight of dispersing agent and / or of grinding aid, when the acrylic ethylene acid is neutralized with the 2-amino acid. 2-methyl-1-propanol. The process according to the invention is also characterized because the amount by weight of acrylic ethylene acid is approximately equal to half the amount by weight of dispersing agent and / or aid in grinding, when the ethylene acrylic acid is neutralized with sodium. Another object of the invention lies in suspensions and / or aqueous dispersions of pigments and / or mineral materials, characterized in that they are obtained by the process according to the invention. Another object of the invention lies in suspensions and / or aqueous dispersions of pigments and / or mineral materials characterized in that they include calcium carbonate, at least one salt of ethylene acrylic acid, and in that they have a solids content higher than 65%, preferably greater than 70%, most preferably greater than 75%, even more preferably between 75 and 78% of its total weight. These dispersions and / or aqueous suspensions are also characterized in that the mineral materials and / or the pigments have an average diameter of less than 50 μm, preferably internal to 15 μm, very preferably less than 5 μm, and even more preferably in that this average diameter is included between 0.3 and 1.7 μm, even more preferably between 0.5 and 0.9 μm, measured by a Sedigraph ™ 5100 device marketed by the company MICROMERITICS ™.

These dispersions and / or aqueous suspensions are also characterized in that they have a fraction of particles with a diameter of less than 2 μm greater than 60% (measured by a Sedigraph ™ 5100 apparatus marketed by the company MICROMERITICS ™), or a fraction of particles with a diameter of less than 2 μm greater than 90% (measured by a Sedigraph ™ 5100 device marketed by the company M1CROMERITICS ™), or a fraction of particles less than 2 μm in diameter greater than 99% (measured by a Sedigraph ™ 5100 device) marketed by the company MICROMERITICS ™). These dispersions and / or aqueous suspensions are also characterized in that they have a Brookfield ™ viscosity measured at 100 revolutions / minute (at 25 ° C, with the mobile n ° 3, with the DVII + device, in a 1 liter container) lower than 1,000 rnPa.s, preferably less than 700 mPa.s, very preferably less than 500 mPa.s, and even more preferably in that this viscosity is included between 100 and 300 mPa.s. These aqueous dispersions and / or suspensions are also characterized in that they have a residue on screens greater than 45 μm, less than 100 ppm, preferably less than 70 ppm, more preferably less than 60 ppm, and more preferably less than 50 ppm. These dispersions and / or aqueous suspensions also they are characterized in that the salt of ethylene acrylic acid is a soluble salt in aqueous medium. These dispersions and / or aqueous suspensions are also characterized in that the carboxylic groups of the ethylene acrylic acid salt are partially or totally dissociated from their acid proton. These dispersions and / or aqueous suspensions are also characterized in that in the ethylene acrylic acid salt, the mass ratio of ethylene monomer with acrylic acid monomer is included between 10: 90 and 30: 70, and is preferably equal to 20: 80. These dispersions and / or aqueous suspensions are also characterized in that the salt of ethylene acrylic acid has a melt index included between 50 g / 10 minutes and 1,500 g / 10 minutes, preferably between 200 g / 10 minutes and 300 g / 10 minutes when the ethylene acrylic acid salt is completely neutralized, and preferably between 1,000 g / 10 minutes and 1,400 g / 10 minutes when the salt of ethylene acrylic acid is neutralized from 70 to 99% (in fraction of the carboxylic sites), measured according to ASTM1238 125 ° C / 2.16kg. These dispersions and / or aqueous suspensions are also characterized in that the carboxylic groups of the ethylene acrylic acid salts are completely neutralized or neutralized from 70% to 99% with respect to the totality of the carboxylic sites of ethylene acrylic acid, with at least one neutralizing agent. These dispersions and / or aqueous suspensions are also characterized in that said neutralizing agent includes at least one monovalent cation. These dispersions and / or aqueous suspensions are also characterized in that said monovalent cation includes one or more alkali ions and / or one or more amines and / or ammonia. These dispersions and / or aqueous suspensions are also characterized in that said alkali monovalent ion includes a sodium ion. These dispersions and / or aqueous suspensions are also characterized in that the amine includes a primary amine. These aqueous dispersions and / or suspensions are also characterized in that the amine includes an alkanolamine, which includes at least one ethanol and / or propanol grouping, and in which the alkanolamine is then preferably chosen from 2-amino-2-methyl-1. -propanol and / or dimethylethanolamine, and in which 2-amino-2-methyl-1-propanol is most preferably. These dispersions and / or aqueous suspensions are also characterized in that an amount of 2-amino-2-methyl-1-propanol is used, in order to provide a fraction of the monovalent cation included between 75 and 125% of the carboxyl groups of the ethylene acrylic acid, and preferably in order to provide a cation fraction monovalent equal to 100% of the carboxyl groups of ethylene acrylic acid. These aqueous dispersions and / or suspensions are also characterized in that an amount of dimethylethanolamine is used, in order to provide a monovalent cation fraction including between 75 and 125% of the carboxylic groups of ethylene acrylic acid, and preferably for the purpose of provide a fraction of monovalent cation equal to 100% of the carboxyl groups of ethylene acrylic acid. These dispersions and / or aqueous suspensions are also characterized in that said ethylene acrylic acid has a viscosity of 3,000 to 25,000 mPa.s, from 15,000 to 100,000 mPa.s, and from 50,000 to 400,000 mPa.s at respective temperatures of 200 ° C, 170 ° C and 140 ° C. These aqueous dispersions and / or suspensions are also characterized in that said ethylene acrylic acid exhibits a viscosity of 3,000 to 7,000 mPa.s, from 15,000 to 20,000 mPa.s, and from 50,000 to 100,000 mPa.s at respective temperatures of 200 ° C, 170 ° C and 140 ° C. These dispersions and / or aqueous suspensions are also characterized in that said ethylene acrylic acid has a viscosity of 15,000 to 25,000 mPa.s, from 50,000 to 100,000 mPa.s, and from 300,000 to 400,000 mPa. s at respective temperatures of 200 ° C, 170 ° C and 140 ° C.

Another object of the invention lies in the dry pigments obtained by the process according to the invention (ie after drying step d)). These dry pigments are also characterized in that they contain calcium carbonate, at least one salt of ethylene acrylic acid and whose calcium carbonate particles have an average diameter of less than 50 μm, preferably less than 15 μm, most preferably less than 5 μm, and even more preferably in that this average diameter is included between 0.3 and 1.7 μm, and even more preferably included between 0.5 and 0.9 μm (measured by a Sedigraph ™ 5100 apparatus marketed by the company MICROMERITICS ™). These dry pigments are also characterized in that the calcium carbonate particles have a particle fraction with a diameter of less than 2 μm greater than 60% (as measured by a Sedigraph ™ 5100 apparatus marketed by the company MICROMERITICS ™), or a fraction thereof. particles with a diameter less than 2 μm greater than 90% (measured by a Sedigraph ™ 5100 sold by the company MICROMERITICS ™), or a fraction of particles smaller than 2 μm in diameter greater than 99% (measured by a Sedigraph device) ™ 5100 marketed by the company MICROMERITICS ™). Another object of the invention lies in the use of the aqueous dispersions and suspensions according to the invention, as well as as dry pigments according to the invention, in the fields of paper, plastics and paints, in particular in the mass of paper and plastic, and in the coating of paper and plastic. EXAMPLES Example 1 This example illustrates the process according to the invention, in which a natural calcium carbonate is treated by a salt of ethylene acrylic acid during a stage of grinding in an aqueous medium, introducing a dispersing agent during the grinding step. Therefore, this example begins by describing the copolymers of ethylene acrylic acid used, then the manufacture of some of its salts. Note: all the granulometric characteristics of the calcium carbonate suspensions were measured from a device of the Sedigraph ™ 5100 type marketed by the company MICROMERITICS ™. Copolymer of acrylic ethylene acid a) This copolymer designates a copolymer of ethylene acrylic acid composed of 20% by weight of acrylic acid and 80% by weight of ethylene. Copolymer of ethylene acrylic acid b) This copolymer means a copolymer of ethylene acrylic acid composed of 20% by weight of acrylic acid and by 80% by weight of ethylene. This copolymer has a melt index of 1,300 g / 10 minutes, measured according to ASTM 1238 125 ° C / 2.16 kg. It is well known that a high melt index corresponds to a low molecular weight. Copolymer of acrylic ethylene acid c) This copolymer refers to a copolymer of ethylene acrylic acid composed of 20% by weight of acrylic acid and 80% by weight of ethylene. This copolymer has a melt index of 300 g / 10 minutes, measured according to ASTM 1238 125 ° C / 2.16 kg. The viscosities (mPa.s) of these different copolymers are indicated in Table 1, as a function of temperature. These rheological properties provide a basis for comparing the molecular weights of these copolymers: a low viscosity indicates a low molecular weight. These viscosity values were measured at the temperatures indicated below with a rheometer marketed under the name MCR 300 by the company PHYSICA ™ with the following conditions: cone-flat rheometer CP50-1, with a constant shear rate equal to 5 s " 1, in a temperature range from 200 ° C to 120 ° C, per step of 0.0833 ° C / s. Table 1: viscosities of the different copolymers of ethylene acrylic acid as a function of temperature.

Acrylic Ethylene Acid Solution No. 1 500 grams of copolymer a) are added in 2.5 liters of deionized water in an ESCO 10 liter reactor. Under stirring, 123.7 grams of 2-amino-2-methyl-1-propanol (so that the carboxylic acid sites of ethylene acrylic acid are neutralized to 100%) were added and the mixture was heated for 1 hour at 98 ° C. . A clear and clear solution is thus obtained. Acrylic Ethylene Acid Solution No. 2 500 grams of copolymer a) are added in 2.5 liters of deionized water in a 10 liter type reactor ESCO. Under agitation, 130.2 grams of dimethylethanolamine (so that they are neutralized to 100 % the carboxylic acid sites of ethylene acrylic acid) were added and the mixture was heated for 1 hour at 98 ° C. A clear and clear solution is thus obtained. Ethylene Acrylic Acid Solution No. 3 500 grams of copolymer b) are added in 5 liters of deionized water in a 10 liter ESCO reactor. Under agitation, 38.8 grams of soda (so that the carboxylic acid sites of ethylene acrylic acid are neutralized to 75%) were added and the mixture was heated for 1 hour at 98 ° C. A clear and clear solution is thus obtained. Acrylic ethylene solution No. 4 500 grams of copolymer b) are added in 5 liters of deionized water in a 10 liter ESCO reactor. Under agitation, 55.4 grams of soda (so as to neutralize all of the carboxylic acid sites of ethylene acrylic acid) were added and the mixture was heated for 1 hour at 98 ° C. A clear and clear solution is thus obtained.

Acrylic ethylene acid solution No. 5 500 grams of copolymer c) are added in 5 liters of deionized water in a 10 liter ESCO reactor. Under stirring, 54.1 grams of soda (so as to neutralize all of the carboxylic acid sites of ethylene acrylic acid) were added and the mixture was heated for 1 hour at 98 ° C. A clear and clear solution is thus obtained. Acrylic ethylene solution No. 6 500 grams of copolymer b) are added in 2.5 liters of deionized water in a 10-liter ESCO reactor. Under agitation, 200 grams of ammonia (so that the carboxylic acid sites of ethylene acrylic acid are neutralized to 100%) were added and the mixture was heated for 1 hour at 98 ° C. A clear and clear solution is thus obtained. Essay No. 1 This essay illustrates the prior art. A Norwegian marble is used whose mean diameter of the particles is equal to 45 μm. This marble has been ground in a watery medium in a 1.4 liter Dynomill ™ type mill with 2,700 grams of grinding balls based on diameter zirconium dioxide included between 0.6 and 1 mm, and in the presence of 0.65% by dry weight of a homopolymer of acrylic acid neutralized by sodium and magnesium and of molecular weight equal to 5,400 g / mol, with respect to the dry weight of marble. Grinding requires 11 minutes / kg. An aqueous suspension of marble is obtained whose solids content is equal to 75.5%, and whose particle size is such that 90% by weight of them have a diameter of less than 2 μm. Brookfield ™ viscosity measured at 25 ° C and at 100 turns / minute with mobile number 3 is 251 mPa. s. This viscosity is measured with a DVII + device, in a 1 liter container; This procedure will be used in the other tests. The residue on a sieve higher than 45 μm was 40 ppm. Essay No. Ib This essay illustrates the prior art. A Norwegian marble is used whose mean diameter of the particles is equal to 45 μm. This marble has been ground in a watery medium in a 1.4 liter Dynomill ™ type mill with 2,700 grams of grinding balls based on zirconium dioxide of diameter included between 0.6 and 1 mm, in the presence of 1.0% dry weight of the Acrylic ethylene solution n ° 6.

An aqueous suspension of marble is obtained whose solid content is equal to 38.0%, and whose particle size is such that 73% by weight of them have a diameter of less than 2 μm. It was impossible to increase the solids content, without altering the viscosity as indicated below. The Brookfield ™ viscosity measured at 25 ° C and at 100 turns / minute with the mobile number 3 is included between 250 and 600 mPa.s. Test No. 2 This test illustrates the invention. A Norwegian marble is used whose mean diameter of the particles is equal to 45 μm. This marble has been ground in a watery medium in a 1.4 liter Dynomill ™ type mill with 2,700 grams of grinding balls based on zirconium dioxide with a diameter between 0.6 and 1 mm, in the presence of 0.67% dry weight of a homopolymer of acrylic acid neutralized by sodium and magnesium and of molecular weight equal to 5,400 g / mol, with respect to the dry weight of marble, and in the presence of 0.5% by dry weight of the solution of ethylene acrylic acid No. 1. An aqueous suspension of marble is obtained whose solids content is equal to 75.7%, and whose particle size is such that 89% by weight of them have a diameter of less than 2 μm.

The Brookfield viscosity measured at 25 ° C and at 100 turns / minute with mobile number 3 is 150 mPa.s. The residue on a sieve higher than 45 μm was 13 ppm. Test No. 3 This test illustrates the invention. A Norwegian marble is used whose mean diameter of the particles is equal to 45 μm. This marble has been ground in a watery medium in a 1.4-liter Dynomill ™ mill with 2,700 grams of grinding balls based on zirconium dioxide diameter included between 0.6 and 1 mm, in the presence of 1.04% by dry weight of a homopolymer of acrylic acid neutralized by sodium and magnesium and of molecular weight equal to 5,400 g / mol, with respto the dry weight of marble, and in the presence of 0.5% by dry weight of the ethylene acrylic acid solution No. 2. Grinding requires 11.3 minutes / kg. An aqueous suspension of marble is obtained whose solid content is equal to 76.1%, and whose particle size is such that 92% by weight of them have a diameter of less than 2 μm. The Brookfield ™ viscosity measured at 25 ° C and at 100 turns / minute with mobile number 3 is 157 mPa. s. Test No. 4 This test illustrates the invention.

A Norwegian marble is used whose mean diameter of the particles is equal to 45 μm. This marble has been ground in a watery medium in a 1.4 liter Dynomill ™ mill with 2,700 grams of grinding balls based on zirconium dioxide with a diameter between 0.6 and 1 mm, in the presence of 1.00% dry weight of a homopolymer of acrylic acid neutralized by sodium and magnesium and of molecular weight equal to 5,400 g / mol, with respect to the dry weight of marble, and in the presence of 0.5% by dry weight of the solution of ethylene acrylic acid No. 3. An aqueous suspension of marble is obtained whose solids content is equal to 74.1%, and whose particle size is such that 90% by weight of them have a diameter of less than 2 μm. The Brookfield ™ viscosity measured at 25 ° C and at 100 turns / minute with mobile number 3 is 153 mPa.s. The residue on a sieve higher than 45 μm was 59 ppm. Test No. 5 This test illustrates the invention. A Norwegian marble is used whose mean diameter of the particles is equal to 45 μm. This marble has been ground in a watery medium in a 1.4 liter Dynomill ™ type mill with 2,700 grams of grinding balls based on diameter zirconium dioxide included between 0.6 and 1 mm, in the presence of 1.00% by dry weight of a homopolymer of acrylic acid neutralized by sodium and magnesium and of molecular weight equal to 5,400 g / mol, with respect to the dry weight of marble, and in the presence 0.5% by dry weight of the solution of ethylene acrylic acid No. 4. An aqueous suspension of marble is obtained whose solid content is equal to 77.0%, and whose particle size is such that 91% by weight of them They have a diameter less than 2 μm. The Brookfield ™ viscosity measured at 25 ° C and at 100 turns / minute with mobile number 3 is 157 mPa. s. Test No. 6 This test illustrates the invention. A Norwegian marble is used whose mean diameter of the particles is equal to 45 μm. This marble has been ground in a watery medium in a 1.4 liter Dynomill ™ mill with 2,700 grams of grinding balls based on zirconium dioxide with a diameter between 0.6 and 1 mm, in the presence of 1.00% dry weight of a homopolymer of acrylic acid neutralized by sodium and magnesium and of molecular weight equal to 5,400 g / mol, with respect to the dry weight of marble, and in the presence of 0.5% by dry weight of the solution of ethylene acrylic acid No. 5. An aqueous suspension of marble is obtained whose solid content is equal to 76.9%, and whose size of the The particles are such that 89% by weight of them have a diameter of less than 2 μm. The Brookfield ™ viscosity measured at 25 ° C and at 100 turns / minute with the mobile number 3 is 187mPa.s. The results demonstrate that the process of the invention leads to suspensions of calcium carbonate treated with an ethylene acrylic acid salt and a dispersing agent, having a high solids content, and in particular greater than 75%. In addition, this solids content is higher than that obtained in. the process framework according to the prior art, and the Brookfield ™ viscosities measured at 25 ° C and at 100 turns / minute are lower than those obtained in the case of the prior art. Furthermore, it has been shown that grinding is also effective with or without acrylic ethylene acid, by comparison between the tests n ° la and 3. Furthermore, no example according to the invention has presented any problem of foam creation in the carbonate suspension of calcium. On the other hand, it has been found that the residues on sieves obtained in the case of the invention were truly negligible. Test No. 7 This test illustrates the prior art.

A polyethylene of high density of the company BASELL ™ POLYOLEFINS commercialized with the name Hostalen ™ GM 9240 HT has been introduced in a kneader of cylinders commercialized with the name Walzwerk 150x400 of the society DR. COLLIN Next, plates of 2 and 4 mm thickness were formed in a press "Testing Platen Presses Type P" P300-P of the company DR. COLLIN Test n ° 8 This test illustrates the invention The suspension of the test n ° 5 has been dried with an MSD ™ 100 sprayer from NIRO ™, a dry treated marble whose particle size is 88% Their weight is less than 2 μm in diameter., the treated and dry marble has been mixed at 180 ° C with a high density polyethylene of the company BASELL ™ POLYOLEFINS marketed under the name Hostalen ™ GM 9240 HT in a cylinder mixer marketed under the name Walzwerk 150x400 of the company DR. COLLIN The composition of the mixture is equimatic in treated product and in high density polyethylene. Next, plates of 2 and 4 mm thickness were formed in a press "Testing Platen Presses Type P" P300-P of the company DR. COLLIN The tensile strengths of the plates For tests 7 and 8, they are respectively 23.9 N / mm2 and 24.2 N / mm2 according to DIN 53455. It is observed that the substitution of the polyethylene by the pigment according to the invention does not reduce the resistance to the traction. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (64)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. Process for the preparation of at least one mineral material and / or at least one pigment that includes natural calcium carbonate and / or precipitate, preferably natural at the same time partially organophilic and partially hydrophilic, characterized in that it includes the steps of: a) supplying at least one mineral material and / or a pigment including natural calcium carbonate and / or precipitate, preferably natural, in dry or in the form of a dispersion and / or of an aqueous suspension, b) optionally milling in dry and / or aqueous medium the mineral material and / or the pigment resulting from step a) c) treating the mineral matter and / or the pigment resulting from step a) and / or step b) d) optionally drying the mineral matter and / or the pigment resulting from step a) and / or b) and / or c) wherein: step c) of treatment corresponds to a stage of m in aqueous medium and / or grinding in aqueous medium, and / or concentration in medium water, the mineral material and / or the pigment from step a) and / or from step b), in the presence of at least one salt of ethylene acrylic acid, - a dispersing and / or aid agent for grinding it is introduced before and / or during the treatment step c). Process according to claim 1, characterized in that the salt of ethylene acrylic acid is a salt soluble in aqueous medium. Process according to any of claims 1 or 2, characterized in that the carboxylic groups of the salt of ethylene acrylic acid are partially or completely dissociated from its acid proton. Process according to any of claims 1 to 3, characterized in that, in the ethylene acrylic acid salt, the mass ratio of ethylene monomer to acrylic acid monomer is included between 10: 90 and 30: 70, and is preferably equal to 20: 80. 5. Process according to any of claims 1 to 4, characterized in that the ethylene acrylic acid salt has a melt index included between 50 g / 10 minutes and 1,500 g / 10 minutes, preferably between 200 g / 10 minutes and 300 g / 10 minutes when the ethylene salt Acrylic is completely neutralized, and preferably between 1,000 g / 10 minutes and 1,400 g / 10 minutes when the salt of ethylene acrylic acid is neutralized from 70 to 99% (in fraction of carboxylic sites), measured according to ASTM1238 125 ° C /2.16 kg. Process according to any of claims 1 to 5, characterized in that the carboxylic groups of the ethylene acrylic acid salts are completely neutralized or neutralized from 70% to 99% with respect to all the carboxylic sites of the ethylene acrylic acid , with at least one neutralization agent. Process according to claim 6, characterized in that the neutralizing agent includes at least one monovalent cation. Process according to claim 7, characterized in that the monovalent cation includes one or more alkali and / or one or more amines and / or ammonia. 9. Process according to claim 8, characterized in that the alkali monovalent ion includes a sodium ion. 10. Process according to claim characterized in that the amine includes a primary amine. 11. Process according to claim 10, characterized in that the amine includes an alkanolamine, which includes at least one ethanol and / or propanol grouping, and in which the alkanolamine is then chosen preferably between the 2-amino-2-methyloxylamine. 1-propanol and / or dimethylethanolamine, and in which 2-amino-2-methylo-1-propanol is most preferably. Process according to claim 11, characterized in that an amount of 2-amino-2-methyl-1-1-propanol is used, in order to provide a fraction of monovalent cation included between 75 and 125% of the groupings carboxylic acids of ethylene acrylic, and preferably in order to provide a monovalent cation fraction equal to 100% of the carboxylic groups of ethylene acrylic acid. Process according to claim 11, characterized in that an amount of dimethylethanolamine is used, in order to provide a monovalent cation fraction including between 75 and 125% of the carboxylic groups of ethylene acrylic acid, and preferably for the purpose of provide a fraction of monovalent cation equal to 100 % of carboxyl groups of ethylene acrylic acid. 14. Process according to any of claims 1 to 13, characterized in that the acrylic ethylene acid has a viscosity of 3,000 to 25,000 mPa.s, from 15,000 to 100,000 mPa.s, and from 50,000 to 400,000 mPa. Sa respective temperatures of 200 ° C, 170 ° C and 140 ° C 15. Process according to claim 14, characterized in that the ethylene acrylic acid has a viscosity of 3,000 to 7,000 mPa.s, from 15,000 to 20,000 mPa.s, and from 50,000 to 100,000 mPa. s at respective temperatures of 200 ° C, 170 ° C and 140 ° C. 16. Process according to claim 14, characterized in that the acrylic ethylene acid has a viscosity of 15,000 to 25,000 mPa.s, from 50,000 to 100,000 mPa.s, and from 300,000 to 400,000 mPa. s at respective temperatures of 200 ° C, 170 ° C and 140 ° C. Process according to claim 1, characterized in that the mineral matter and / or the pigment includes, in addition to the calcium carbonate, also at least one other mineral material and / or pigment selected from among the dolomites, Bentonites, kaolin, talc, cement, plaster, lime, magnesia, titanium dioxide, white satin, aluminum trioxide or even aluminum trihydroxide, silicas, mica and the mixture of these charges between them, such as talc-calcium carbonate, calcium carbonate-kaolin mixtures, or even calcium carbonate mixtures with aluminum trihydroxide or aluminum trioxide, or even mixtures with synthetic or natural fibers or even the structures of minerals such as talc-calcium carbonate or talc-titanium dioxide, or their mixtures, and in which Another mineral material is preferably kaolin. 18. Process according to any of claims 1 to 17, characterized in that the dry weight amount of calcium carbonate is greater than or equal to 70% by total dry weight of pigments and / or mineral materials. 19. Process according to any of claims 1 to 18, characterized in that, during stage a) and when the mineral matter and / or the pigment is present in the form of a dispersion and / or an aqueous suspension, the concentration in dry weight of pigment and / or mineral matter is greater than 60%, preferably 65%, most preferably greater than 70%, and even more preferably 74% to 78% of the total weight of the dispersion and / or suspension or, in that the dry weight concentration of pigment and / or mineral matter is less than 30%, preferably including between 18 and 22% of the total weight of the dispersion and / or suspension, and that the dispersion and / or suspension is a suspension that It does not contain dispersing agent. Process according to any of claims 1 to 19, characterized in that the grinding step b) is carried out continuously or discontinuously, preferably continuously. Process according to any one of claims 1 to 20, characterized in that the grinding step b) is carried out in the presence of grinding balls based on oxide and / or zirconium silicate, optionally stabilized with a coarse oxide. and / or yttrium. 22. Process according to any of claims 1 to 21, characterized in that the grinding step b) is a dry milling leading to the production of mineral materials and / or pigments having an average diameter of less than 50 μm , preferably less than 15 μm, very preferably less than 5 μm, and even more preferably in that this average diameter is included between 1.3 and 1.7 μm. 23. Process of compliance with any of the claims 1 to 21, characterized in that the grinding step b) is a grinding in an aqueous medium leading to the production of mineral materials and / or pigments having a fraction of particles with a diameter of less than 2 μm greater than 60% ( measured by a Sedigraph ™ 5100 device marketed by MICROMERITICS ™), or a fraction of particles with a diameter less than 2 μm greater than 90% (measured by a Sedigraph ™ 5100 device marketed by MICROMERITICS ™), or a fraction of particles with a diameter less than 2 μm greater than 99% (measured by a Sedigraph ™ 5100 device marketed by the company MICROMERITICS ™). 24. Process according to any of claims 1 to 23, characterized in that the treatment step c) occurs in aqueous medium, and leads to a dispersion and / or an aqueous suspension whose percentage by dry weight of mineral materials and / or of pigments is greater than 65%, preferably greater than .70%, very preferably greater than 75%, and even more preferably between 75% and 78% of the total weight of the dispersion and / or suspension. 25. Process according to any of claims 1 to 24, characterized in that the treatment step c) leads to a dispersion and / or an aqueous suspension whose mineral matters and / or the pigments have an average diameter of less than 50 μm, preferably less than 15 μm, very preferably less than 5 μm, and still more preferably in that this average diameter is included between 0.3 and 1.7 μm, and according to the most preferred way in which this average diameter is included between 0.5 and 0.9 μm, measured by a Sedigraph ™ apparatus 5100 marketed by the company M1CROMERICTICS ™. 26. Compliance process with any of the. claims 1 to 25, characterized in that the treatment step c) leads to a dispersion and / or an aqueous suspension having a fraction of particles with a diameter less than 2 μm greater than 60% (measured by a Sedigraph ™ 5100 apparatus marketed by the MICROMERITICS ™ company), or a fraction of particles with a diameter smaller than 2 μm greater than 90% (measured by a Sedigraph ™ 5100 device marketed by the company MICROMERITICS ™), or a particle fraction with a diameter smaller than 2 μm greater than 99% (measured by a Sedigraph ™ 5100 device marketed by MICROMERITICS ™). 27. Process according to any of claims 1 to 26, characterized in that the step c) of treatment leads to a dispersion and / or an aqueous suspension having a Brookfield ™ viscosity measured at 100 revolutions / minute (at 25 ° C with mobile number 3, and with the DVII + device in a 1 liter container) less than 1,000 mPa.s, preferably less than 700 mPa.s, most preferably less than 500 mPa.s, and even more preferably in that this viscosity is included between 100 and 300 mPa. s. 28. Process according to any of claims 1 to 27, characterized in that the step c) of treatment leads to a dispersion and / or an aqueous suspension having a residue on screens greater than 45 μm, less than 100 ppm, preferably less than 70 ppm, more preferably less than 60 ppm, and even more preferably less than 50 ppm. 29. Process according to any of claims 1 to 28, characterized in that step c) is preferably a step of grinding in an aqueous medium. Process according to any one of claims 1 to 29, characterized in that the drying step d) is preferably carried out after step c) of treatment. 31. Process according to any of claims 1 to 30, characterized in that the drying is performed by an atomizer dryer 32. Process according to any of claims 1 to 30, characterized in that the dispersing agent and / or aid to the grinding in an aqueous medium introduced during and / or before step c) is a homopolymer of acrylic acid and / or an acid copolymer acrylic with another water-soluble monomer chosen from methacrylic acid, maleic acid, itaconic acid, crotonic acid, fumaric acid, isocrotonic acid, aconitic, mesaconic, sinapic, undecylenic, angelic, canonic and / or 2-acrylamido acid 2-methyl propanesulfonic acid or partially neutralized formor even between acrylamide, methylacrylamide, esters of acrylic or methacrylic acids, such as ethylene or propylene glycol acrylate or methacrylate phosphate or even between vinylpyrrolidone, vinylcaprolactam, vinyl acetate, sodium styrene sulfonate, the allylamine and its derivatives, and preferably in that the dispersing and / or aiding agent is chosen from the copolymers of acrylic acid with acrylamide or maleic acid. 33. Process according to any of claims 1 to 32, characterized in that the dry milling agent used during step b) when it is a dry grinding, is chosen from the glycol-based compounds, and preferably between ethylene glycol, diethylene glycol, monopropylene glycol, and because it is preferably a monopropylene glycol with molecular weight included between 200 and 1,000 g / mol. 34. Process according to any of claims 1 to 33, characterized in that the total proportion of ethylene acrylic acid is included between 0.1 and 10% preferably between 0.2 and 2%, and most preferably between 0.5 and 1% of the dry weight of the pigments and / or mineral materials. 35. Process according to any of claims 1 to 34, characterized in that the total proportion of dispersant and / or grinding aid agent is included between 0.1 and 2% preferably between 0.2 and 1.5%, and most preferably between 0.3 and 0.6% of the dry weight of the pigments and / or mineral materials. 36. Process according to any of claims 1 to 35, characterized in that the amount by weight of acrylic ethylene acid is approximately equal to the amount by weight of dispersing agent and / or grinding aid, when the ethylene acrylic acid is neutralizes with 2-amino-2-methyl-1-propanol. 37. Process according to any of claims 1 to 36, characterized in that the weight amount of acrylic ethylene acid is approximately equal to half the amount by weight of dispersing agent and / or grinding aid, when the acid Acrylic ethylene is neutralized with sodium. 38. Suspensions and / or aqueous dispersions of pigments and / or mineral materials,. characterized in that they are obtained by the process according to one of claims 1 to 37. 39. Suspensions and / or aqueous dispersions of pigments and / or mineral materials characterized in that they include calcium carbonate, at least one salt of ethylene acrylic acid and because they have a solids content higher than 65%, preferably higher than 70%, very preferably greater than 75%, and even more preferably between 75 and 78% of its total weight. 40. Aqueous suspensions and / or dispersions of pigments and / or mineral materials according to claim 39, characterized in that the mineral materials and / or the pigments have an average diameter of less than 50 μm, preferably less than 15 μm, very preferably less than 5 μpv, and even more preferably in that this average diameter is included between 0.3 and 1.7 μm, and more preferably between 0.5 and 0.9 μm, measured by a Sedigraph ™ 5100 device marketed by the company MICROMERITICS ™. 41. Aqueous suspensions and / or dispersions of pigments and / or mineral materials according to any of claims 39 or 40, characterized in that they have a fraction of particles with a diameter of less than 2 μm greater than 60% (measured by an apparatus Sedigraph ™ 5100 marketed by the company MICROMERITICS ™), or a fraction of particles with a diameter less than 2 μm greater than 90% (measured by a Sedigraph ™ 5100 device marketed by the company MICROMERITICS ™), or a particle fraction with a diameter less than 2 μm greater than 99% (measured by a Sedigraph ™ 5100 device marketed by MICROMERITICS ™). 42. Aqueous suspensions and / or dispersions of pigments and / or mineral materials according to any of claims 39 to 41, characterized in that they have a Brookfield ™ viscosity measured at 100 revolutions / minute (and at 25 ° C with the mobile no. 3 with the DVII + apparatus in a 1 liter container) of less than 1,000 mPa.s, preferably less than 700 mPa.s, very preferably less than 500 mPa.s, and even more preferably in which this viscosity is included among 100. and 300 mPa. s. 43. Aqueous suspensions and / or dispersions of pigments and / or mineral materials according to any of claims 39 to 42, characterized in that they have a sieve residue greater than 45 μm, less than 100 ppm, preferably less than 70 ppm , most preferably less than 60 ppm, and even more preferably less than 50 ppm. 44. Aqueous suspensions and / or dispersions of pigments and / or mineral materials according to any of claims 39 to 43, characterized in that the salt of ethylene acrylic acid is a salt soluble in aqueous medium. 45. Aqueous suspensions and / or dispersions of pigments and / or mineral materials according to any of claims 39 to 44, characterized in that the carboxyl groups of the ethylene acrylic acid salt are partially or totally dissociated from its acid proton. 46. Aqueous suspensions and / or dispersions of pigments and / or mineral materials according to any of claims 39 to 45, characterized in that in the ethylene acrylic acid salt, the mass ratio of ethylene monomer to acrylic acid monomer is included between 10: 90 and 30: 70, and is preferably equal to 20: 80. 47. Aqueous suspensions and / or dispersions of pigments and / or mineral materials according to one of claims 39 to 46, characterized in that the salt of Acrylic ethylene acid has a melt index included between 50 g / 10 minutes and 1,500 g / 10 minutes, preferably between 200 g / 10 minutes and 300 g / 10 minutes when the ethylene acrylic acid salt is completely neutralized, and preferably between 1,000 g / 10 minutes and 1,400 g / 10 minutes when the salt of ethylene acrylic acid is neutralized from 70 to 99% (in fraction of the carboxylic sites), measured according to the ASTM1238 standard 125 ° C / 2.1 6kg 48. Aqueous suspensions and / or dispersions of pigments and / or mineral materials according to any of claims 39 to 47, characterized in that the carboxylic groups of the ethylene acrylic acid salts are completely neutralized or neutralized from 70% to 99% with respect to all the carboxylic sites of ethylene acrylic acid, with at least one neutralizing agent. 49. Aqueous suspensions and / or dispersions of pigments and / or mineral materials according to claim 48, characterized in that the neutralizing agent includes at least one monovalent cation. 50. Aqueous suspensions and / or dispersions of pigments and / or mineral materials according to claim 49, characterized in that the monovalent cation includes one or more alkali and / or one or more amines and / or ammonia. 51. Aqueous suspensions and / or dispersions of pigments and / or mineral materials according to claim 50, characterized in that the alkali monovalent ion includes a sodium ion. 52. Aqueous suspensions and / or dispersions of pigments and / or mineral materials according to claim 50, characterized in that the amine includes a primary amine. 53. Aqueous suspensions and / or dispersions of pigments and / or mineral materials according to claim 52, characterized in that the amine includes an alkanolamine, which includes at least one ethanol and / or propanol group, and in which the alkanolamine is then chosen preferably from 2-amino-2. -methyl-1-propanol and / or dimethylethanolamine, and because 2-amino-2-methyl-1-propanol is most preferably. 54. Aqueous suspensions and / or dispersions of pigments and / or mineral materials according to claim 53, characterized in that an amount of 2-amino-2-methyl-l-propanol is used, in order to provide a fraction of monovalent cation included between 75 and 125% of the carboxylic groups of ethylene acrylic acid, and preferably in order to provide a monovalent cation fraction equal to 100% of the carboxylic groups of ethylene acrylic acid. 55. Aqueous suspensions and / or dispersions of pigments and / or mineral materials according to claim 53, characterized in that an amount of dimethylethanolamine is used, in order to provide a fraction of cation-monovalent included between 75 and 125% of the carboxylic groups of the ethylene acrylic acid, and preferably in order to provide a fraction of monovalent cation equal to 100% of the carboxyl groups of the ethylene acrylic acid. 56. Suspensions and / or aqueous dispersions of pigments and / or mineral materials according to any of claims 39 to 55, characterized in that the acrylic ethylene acid has a viscosity of 3,000 to 25,000 mPa.s, from 15,000 to 100,000 mPa.s, and from 50,000 to 400,000 mPa.s at respective temperatures of 200 ° C, 170 ° C and 140 ° C. 57. Aqueous suspensions and / or dispersions of pigments and / or mineral materials according to claim 56, characterized in that the ethylene acrylic acid has a viscosity of 3,000 to 7,000 mPa.s, from 15,000 to 20,000 mPa.s, and 50,000 to 100,000 mPa. s at respective temperatures of 200 ° C, 170 ° C and 140 ° C. 58. Aqueous suspensions and / or dispersions of pigments and / or mineral materials according to claim 56, characterized in that the acrylic ethylene acid has a viscosity of 15,000 to 25,000 mPa.s, from 50,000 to 100,000 mPa.s, and 300,000 to 400,000 mPa. s at respective temperatures of 200 ° C, 170 ° C and 140 ° C. 59. Dry pigments characterized in that they are obtained by the process according to any of claims 1 to 37. 60. Dry pigments according to claim 59, characterized in that they contain calcium carbonate, at least one salt of ethylene acrylic acid and whose Calcium carbonate particles have an average diameter of less than 50 μm, preferably less than 15 μm, very preferably less than 5 μm, and still more preferably in which this average diameter is included between 0.3 and 1.7 μm, and more preferably between 0.5 and 0.9 μm (measured by an apparatus) Sedigraph ™ 5100 marketed by the company MICROMERITICS ™). 61. Dry pigments according to claim 59, characterized in that the calcium carbonate particles have a fraction of particles with a diameter of less than 2 μm greater than 60% (measured by a Sedigraph ™ 5100 device marketed by the company MICROMERITICS ™) , or a fraction of particles with a diameter of less than 2 μm greater than 90% (measured by a Sedigraph ™ 5100 device marketed by the company MICROMERITICS ™), or a fraction of particles with a diameter smaller than 2 μm greater than 99% ( measured by a Sedigraph ™ 5100 device marketed by the company MICROMERITICS ™). 62. Use of aqueous dispersions and suspensions according to any of claims 38 to 58, and of the dry pigments according to any of claims 59 to 61, in the fields of paint, plastics and paper . 63. Use of dispersions and suspensions aqueous as well as dry pigments according to claim 62, in the coating and in the plastic mass. 64. Use of dispersions and aqueous suspensions as well as dry pigments according to claim 62, in the coating and in the mass of the paper.