FR2894847A1 - Aqueous dispersions of mineral matter, useful e.g. in the manufacture of plastic, paint and dental paste, comprises an acrylic acid homopolymer and a fluorinated mineral compound, as dispersing agent - Google Patents

Aqueous dispersions of mineral matter, useful e.g. in the manufacture of plastic, paint and dental paste, comprises an acrylic acid homopolymer and a fluorinated mineral compound, as dispersing agent Download PDF

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FR2894847A1
FR2894847A1 FR0604655A FR0604655A FR2894847A1 FR 2894847 A1 FR2894847 A1 FR 2894847A1 FR 0604655 A FR0604655 A FR 0604655A FR 0604655 A FR0604655 A FR 0604655A FR 2894847 A1 FR2894847 A1 FR 2894847A1
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aqueous dispersions
mineral matter
mineral
acrylic acid
homopolymer
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FR2894847B1 (en
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Christian Jacquement
Jacques Mongoin
Jean Marc Suau
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Coatex SAS
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Coatex SAS
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/64—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/021—Calcium carbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/021—Calcium carbonates
    • C09C1/022—Treatment with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/42—Clays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • C09C3/041—Grinding
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/385—Oxides, hydroxides or carbonates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof

Abstract

Aqueous dispersions of mineral matter, comprises an acrylic acid homopolymer and a fluorinated mineral compound, as dispersing agent.

Description

DISPERSIONS DE MATIERES MINERALES DANS L'EAU ET LEURS UTILISATIONSDISPERSIONS OF MINERAL MATERIALS IN WATER AND USES THEREOF

L'invention porte tout d'abord sur des dispersions aqueuses de matieres minerales, caracterisees en ce qu'elles contiennent comme agent dispersant : - au moins un homopolymere de 1'acide acrylique, et au moins un compose mineral fluore.  The invention relates first of all to aqueous dispersions of mineral matter, characterized in that they contain as dispersing agent: at least one homopolymer of acrylic acid, and at least one fluorinated mineral compound.

Elie concerne egalement leurs utilisations dans des formulations aqueuses contenant des matieres minerales telles que le carbonate de calcium, et notamment dans les domaines du papier et plus particulierement dans le cadre de la fabrication de la feuille de papier et du couchage de la feuille de papier, de la peinture, du plastique et de la cosmetique tel que notamment dans la fabrication de pates dentaires.  Elie also relates to their uses in aqueous formulations containing mineral materials such as calcium carbonate, and in particular in the fields of paper and more particularly in the context of the manufacture of the paper sheet and the coating of the sheet of paper, paint, plastic and cosmetics such as in particular in the manufacture of toothpastes.

L'homme du metier, fabriquant de dispersions et de suspensions aqueuses de matieres minerales telles que notamment le carbonate de calcium, connait depuis fort longtemps l'utilisation d'agents de dispersion et / ou d'aide au broyage A. base d'homopolymeres et / ou de copolymeres acryliques, en vue de maintenir lesdites matieres minerales en suspension dans 1'eau A. des concentrations en matiere seche elevees et ce, de maniere stable dans le temps.  The person skilled in the art, manufacturing aqueous dispersions and suspensions of mineral matter such as in particular calcium carbonate, has known for a very long time the use of dispersion agents and / or grinding aid A. homopolymer base and / or acrylic copolymers, in order to maintain said mineral matter in water suspension A. high concentrations of dry matter and that, in a stable manner over time.

Il connait ainsi les brevets FR 2 603 042, EP 0 100 947, EP 0 127 388, EP 0 129 329 et EP 0 542 644 qui decrivent l'utilisation pour les fins precitees de tels polymeres, totalement ou partiellement neutralises par divers agents de neutralisation, et presentant un poids moleculaire peu eleve.  It thus knows the patents FR 2 603 042, EP 0 100 947, EP 0 127 388, EP 0 129 329 and EP 0 542 644 which describe the use for the aforementioned purposes of such polymers, totally or partially neutralized by various agents of neutralization, and having a low molecular weight.

Dans le cadre de ces memes applications, it connait egalement les brevets FR 2 488 814, EP 0 100 948 et EP 0 542 643 qui enseignent 1'utilisation de la fraction d'homopolymeres et / ou de copolymeres acryliques, dont la viscosite specifique est comprise entre 0,3 et 0,8, telle que mesuree par la methode commune decrite dans les brevets concernes.  In the context of these same applications, it also knows the patents FR 2 488 814, EP 0 100 948 and EP 0 542 643 which teach the use of the fraction of homopolymers and / or acrylic copolymers, the specific viscosity of which is between 0.3 and 0.8, as measured by the common method described in the patents concerned.

Neanmoins, ces differentes solutions qui permettent d'obtenir des suspensions aqueuses de matieres minerales stables dans le temps, ne permettent pas de disperser dans 1'eau et ce, avec des teneurs en poids sec de matieres minerales elevees (superieures ou egales a 65 % du poids total de la dispersion), des particules minerales telles que notamment le carbonate de calcium, lorsque celles-ci sont issues du procede suivant : a) broyage des matieres minerales en milieu aqueux sans usage d'agent dispersant et / ou d'agent d'aide au broyage et a faible concentration en matiere seche (1'extrait sec, ou la teneur en poids sec de matiere minerale etant alors inferieure A. 40 % par rapport au poids total de la suspension), b) puis concentration mecanique et / ou thermique, en vue d'obtenir des dispersions aqueuses de matieres minerales ayant une teneur en matiere seche superieure ou egale a 65 % par rapport au poids total de la dispersion,  Nevertheless, these different solutions which make it possible to obtain aqueous suspensions of minerals which are stable over time, do not make it possible to disperse in water and with dry matter contents of high mineral matter (greater than or equal to 65% of the total weight of the dispersion), mineral particles such as in particular calcium carbonate, when these are derived from the following process: a) grinding the mineral materials in an aqueous medium without the use of dispersing agent and / or agent grinding aid and low concentration of dry matter (the dry extract, or the dry weight content of mineral matter being then less than 40% relative to the total weight of the suspension), b) then mechanical concentration and or thermal, in order to obtain aqueous dispersions of mineral matter having a dry matter content greater than or equal to 65% relative to the total weight of the dispersion,

un agent dispersant etant introduit entre 1'etape a) et 1'etape b), et / ou pendant 1'etape b), et / ou pendant et apres 1' etape b).  a dispersing agent being introduced between step a) and step b), and / or during step b), and / or during and after step b).

Dans la suite de la demande, la Demanderesse pourra faire reference a un tel procede a travers 1'expression "procede de broyage a faible extrait sec sans agent dispersant puis de concentration a haut extrait sec en presence d'agent dispersant".  In the remainder of the application, the Applicant may refer to such a process through the expression "low-solids dry milling process without dispersing agent and high solids concentration concentration in the presence of dispersing agent".

En vue de resoudre ce probleme technique particulier, 1'homme du metier connait le document EP 0 027 996, qui decrit un procede de fabrication de suspensions aqueuses de matieres minerales par une etape de broyage en milieu humide sans agent dispersant, la suspension etant ensuite filtree, et le gateau de filtration alors obtenu est seche ou transforms par addition d'un agent dispersant en une suspension de faible viscosite ; 1'etape de broyage est realisee a une concentration en matiere seche inferieure A. 60 % en poids total de la suspension, et la suspension finale obtenue apres ajout de 1'agent dispersant possede une teneur en matiere seche au moins superieure a 80 % de son poids total.  In order to solve this particular technical problem, one skilled in the art knows the document EP 0 027 996, which describes a process for manufacturing aqueous suspensions of mineral matter by a grinding step in a wet medium without dispersing agent, the suspension being then filtered, and the filtration cake then obtained is dried or converted by adding a dispersing agent in a low viscosity suspension; The grinding step is carried out at a dry matter concentration of less than 60% by total weight of the suspension, and the final suspension obtained after addition of the dispersing agent has a dry matter content of at least 80% by weight. its total weight.

Mais si 1'homme du metier ne choisit pas convenablement 1'agent dispersant qu'il met en oeuvre, it ne parvient pas a obtenir des teneurs finales en matieres seches suffisamment elevees tout en maintenant un caractere manipulable a la suspension obtenue ; or, rien n'est enseigne a 1'homme du metier sur le choix d'agents dispersants particuliers dans ce document EP 0 027 996, ni sur les conditions experimentales a mettre en oeuvre pour obtenir des teneurs en matiere seche si elevees et des viscosites compatibles avec l'utilisation d'une telle suspension : un tel document ne lui permet done pas de resoudre le probleme technique de la presente Demande.  But if a person skilled in the art does not choose suitably the dispersing agent that it implements, it fails to obtain final contents of dry materials sufficiently high while maintaining a manipulable character to the suspension obtained; however, nothing is taught to those skilled in the art on the choice of particular dispersing agents in this document EP 0 027 996, nor on the experimental conditions to be used to obtain high levels of dry matter and viscosities. compatible with the use of such a suspension: such a document does not allow him to solve the technical problem of this Application.

C'est precisement pour cette raison que 2 autres documents, ulterieurs au document EP 0 027 996 ont aborde le mane probleme technique, mais sous 1'angle du choix d'agents de dispersion particuliers, qui permettent de resoudre effectivement le probleme technique de la presente Demande. Nous verrons par la suite que ces documents ne sont pas denues d'inconvenients pour 1'homme du metier.  It is precisely for this reason that two other documents, other than EP 0 027 996, have dealt with the technical problem, but with regard to the choice of particular dispersing agents, which make it possible to effectively solve the technical problem of the this application. We will see later that these documents are not without drawbacks for the person skilled in the art.

Ainsi, 1'homme du metier connait le brevet WO 01 / 048 093, qui enseigne l'utilisation d'homopolymeres et de copolymeres de 1'acide acrylique avec differents monomeres hydrosolubles allyliques et vinyliques, d'un poids moleculaire correspondant a un indice de viscosite allant de 0,08 a 0,80 selon la methode decrite dans la demande de brevet concernee.  Thus, one skilled in the art knows the patent WO 01/048 093, which teaches the use of homopolymers and copolymers of acrylic acid with different water-soluble allylic and vinyl monomers, of a molecular weight corresponding to a viscosity ranging from 0.08 to 0.80 according to the method described in the patent application concerned.

Le brevet EP 0 850 685 lui enseigne une autre solution qui consiste en l'utilisation de copolymeres de l'acide acrylique et de 1'acide maleique, presentant un rapport molaire entre ces deux unites compris entre 2:1 et 10:1, et une masse moleculaire moyenne comprise entre 1 000 et 100 000 Daltons.  EP 0 850 685 teaches another solution which consists in the use of copolymers of acrylic acid and maleic acid, having a molar ratio between these two units of between 2: 1 and 10: 1, and an average molecular mass of between 1,000 and 100,000 Daltons.

Enfin, 1'homme du metier connait aussi le document EP 1 147 061, qui decrit un procede proche de celui evoque plus haut, mais neanmoins different. Ce document decrit en effet un procede caracterise par les etapes de fabrication d'une suspension aqueuse diluee de carbonate dont la teneur en poids ne depasse pas 40 %, puis elimination de 1eau pour obtenir une teneur en poids comprise entre 45 % et 65 %, puis ajout eventuel d'agent dispersant, puis elimination subsequente d'eau sous pression reduite pour augmenter la teneur en poids de 5 % au moins, puis enfin traitement mecanique de la suspension obtenue. Ce procede est done different de celui objet de la presente Demande ; it apparait d'autre part plus complexe a mettre en oeuvre, de part le nombre d'etapes plus important, et la necessite de disposer d'un appareillage permettant de travailler sous pression reduite.  Finally, the person skilled in the art also knows the document EP 1 147 061, which describes a process similar to that mentioned above, but nevertheless different. This document describes a process characterized by the manufacturing steps of a dilute aqueous suspension of carbonate whose content in weight does not exceed 40%, then removal of water to obtain a content by weight of between 45% and 65%, then optional addition of dispersing agent, then subsequent removal of water under reduced pressure to increase the content by weight of at least 5%, and finally mechanical treatment of the suspension obtained. This method is therefore different from that which is the subject of the present Application; it appears on the other hand more complex to implement, due to the number of stages more important, and the need to have an apparatus to work under reduced pressure.

L'homme du metier a aujourd'hui mis au point une solution nouvelle en vue d'obtenir des dispersions aqueuses de particules minerales telles que notamment du carbonate de calcium, ayant un extrait sec eleve (superieur a 65 % en poids de matieres minerale par rapport au poids total de la dispersion) et une viscosite BrookfieldTM immediate mesuree a 100 tours / minute inferieure a 5 000 mPa.s, au cours d'une etape de concentration mecanique et / ou thermique, consecutive a une etape de broyage a faible concentration en matiere seche (inferieure a 40 % en poids de matieres minerale par rapport au poids total de la dispersion), en milieu aqueux et sans usage d'agent dispersant et / ou d'agent d'aide au broyage, ce qu'aucun des documents de fart anterieur ne proposait, a 1'exception des documents WO 01 / 048 093 et EP 0 850 685.  Those skilled in the art today have developed a novel solution for obtaining aqueous dispersions of mineral particles, such as in particular calcium carbonate, having a high solids content (greater than 65% by weight of mineral matter per relative to the total weight of the dispersion) and an instant BrookfieldTM viscosity measured at 100 rpm less than 5000 mPa.s, during a mechanical and / or thermal concentration step, following a low concentration grinding step in dry matter (less than 40% by weight of mineral matter relative to the total weight of the dispersion), in an aqueous medium and without the use of dispersing agent and / or grinding aid agent, which none of the Prior art documents, with the exception of WO 01/04893 and EP 0 850 685, proposed none.

De plus, les documents WO 01 / 048 093 et EP 0 850 685 enseignent entre autres que, des homopolymeres et / ou des copolymeres de 1'acide acrylique, totalement ou partiellement neutralises, ne conviennent pas pour disperser dans 1'eau du carbonate de calcium dans le cadre du procede de broyage a faible extrait sec sans agent dispersant puis de concentration a haut extrait sec en presence d'agent dispersant. Cet enseignement s'entend a 1'exception des homopolymeres et des copolymeres de 1'acide acrylique tres particuliers qui font l'objet des inventions de selection decrites dans les documents WO 01 / 048 093 et EP 0 850 685. Le caractere tres restrictif de ces solutions n'offre pas un grand degre de latitude a 1'homme du metier dans le choix des dispersants qu'il souhaite mettre en oeuvre.  In addition, WO 01/048 093 and EP 0 850 685 teach inter alia that homopolymers and / or copolymers of acrylic acid, which are totally or partially neutralized, are not suitable for dispersing in water calcium in the context of the low-solids dry milling process without dispersing agent and then high solids concentration in the presence of dispersing agent. This teaching has the exception of the very particular homopolymers and copolymers of acrylic acid which are the subject of the selection inventions described in WO 01/048 093 and EP 0 850 685. The very restrictive nature of these solutions do not offer a large degree of latitude to the skilled person in the choice of dispersants he wishes to implement.

Or, et de maniere tout a fait surprenante, la presente invention permet a 1'homme du metier d'utiliser des homopolymeres de 1'acide acrylique et ce, sans aucune restriction a leur encontre. En effet, de maniere inattendue, 1'utilisation d'homopolymeres de 1'acide acrylique en combinaison avec un compose mineral fluore permet justement a 1'homme du metier de disperser du carbonate de calcium selon le procede de broyage a faible extrait sec sans agent dispersant puis de concentration a haut extrait sec en presence d'agent dispersant. L'homme du metier parvient alors a obtenir de maniere surprenante, notamment compte tenu de 1'enseignement prodigue par les documents WO 01 / 048 093 et EP 0 850 685, des extraits secs eleves (superieurs a 65 % en poids de matieres minerale par rapport au poids total de la dispersion) et une viscosite BrookfieldTM immediate mesuree a 100 tours / minute faible (inferieure a 5 000 mPa.$).  Now, and quite surprisingly, the present invention enables the skilled person to use homopolymers of acrylic acid without any restriction on them. In fact, unexpectedly, the use of homopolymers of acrylic acid in combination with a fluorinated mineral compound enables the skilled person to disperse calcium carbonate according to the low solids dry milling method without agent. dispersant and high solids concentration concentration in the presence of dispersing agent. The skilled person then manages to obtain surprisingly, especially in view of the teaching provided by the documents WO 01/04893 and EP 0 850 685, high dry extracts (greater than 65% by weight of mineral matter by relative to the total weight of the dispersion) and an instant Brookfield ™ viscosity measured at 100 rpm low (less than 5000 mPa · $).

Enfin, la presente invention permet a 1'homme du metier d'obtenir, par optimisation du couple forme par 1'homopolymere de 1'acide acrylique et du compose mineral fluore, des solutions qui s'averent, de maniere surprenante, encore plus performantes que celles proposes dans les documents WO 01 / 048 093 et EP 0 850 685 ; certaines des solutions decrites dans la presente Demande permettent en effet a 1'homme du metier d'obtenir des extraits secs tres elev&s (sup&rieurs a 70 % en poids de matieres mineral& par rapport au poids total de la dispersion) et une viscosit& BrookfieldTM immediate mesur&e a 100 tours / minute tres faible (inferieure a 500 mPa.s et parfois meme inferieure a 250 mPa.$), ce qui n'est pas rev&le dans les deux documents WO 01 / 048 093 et EP 0 850 685.  Finally, the present invention makes it possible for one skilled in the art to obtain, by optimizing the couple formed by the homopolymer of acrylic acid and of the fluorinated mineral compound, solutions that surprisingly prove to be even more efficient. than those proposed in the documents WO 01/04893 and EP 0 850 685; some of the solutions described in the present Application allow the skilled person to obtain very high solids (greater than 70% by weight of mineral matter relative to the total weight of the dispersion) and an instant BrookfieldTM viscosity measured at 100 rpm very low (less than 500 mPa.s and sometimes even less than 250 mPa. $), which is not covered in the two documents WO 01/048 093 and EP 0 850 685.

Aussi, le proc&de suivant :Also, the following procedure:

a) preparation d'une suspension aqueuse de matieres minerales par broyage desdites matieres minerales dans 1'eau sans agent dispersant et / ou agent d'aide au broyage, ladite suspension ayant une concentration en poids sec de matieres minerales inferieure ou &gale A. 40 % de son poids total,  a) preparing an aqueous suspension of mineral matter by grinding said mineral material in water without a dispersing agent and / or grinding aid agent, said suspension having a concentration in dry weight of mineral matter less than or equal to A. 40 % of its total weight,

b) concentration de la suspension aqueuse de matieres minerales obtenue au tours de 1'etape a), par des moyens mecaniques et / ou thermiques, en vue d'obtenir une dispersion aqueuse de matieres minerales dont la concentration en poids sec de matieres minerales est au moins &gale a 65 % du poids total de ladite dispersion,  b) concentration of the aqueous suspension of mineral matter obtained in the course of step a), by mechanical and / or thermal means, in order to obtain an aqueous dispersion of mineral matter whose concentration in dry weight of mineral matter is at least 65% of the total weight of said dispersion,

qui met en oeuvre :which implements:

au moins un agent dispersant introduit entre 1'&tape a) et 1'etape b), et / ou pendant l'etape b), et / ou pendant et apres 1'etape b), - sous la forme d'une combinaison : - d'au moins un homopolymere de 1'acide acrylique, - et d'au moins un compose mineral fluor&.  at least one dispersing agent introduced between step a) and step b), and / or during step b), and / or during and after step b), in the form of a combination: at least one homopolymer of acrylic acid, and at least one fluorine mineral compound.

30 a permis a la Demanderesse de mettre au point le premier objet de 1'invention, qui consiste donc en des dispersions aqueuses de matieres minerales, caract&risees en ce qu'elles contiennent comme agent dispersant : au moins un homopolymere de 1'acide acrylique, et au moins un compose mineral fluor&. 15 20 25 35 Dans le domaine des dispersions aqueuses de carbonate de calcium, la Demanderesse connait l'usage de composes mineraux fluores.  Has allowed the Applicant to develop the first object of 1'invention, which is therefore aqueous dispersions of minerals, characterized in that they contain as dispersing agent: at least one homopolymer of acrylic acid, and at least one fluorine mineral compound. In the field of aqueous dispersions of calcium carbonate, the Applicant knows the use of fluorescent mineral compounds.

Ainsi, le document US 3 179 493 enseigne la fabrication d'un carbonate de calcium precipite, finement divise et de haute purete, par reaction entre un sel de calcium et un compose carbonate et ce, en presence d'un compose fluore choisi parmi les fluorures et les silicofluorures de potassium, de sodium et d'ammonium. Quant au document US 3 793 047, it enseigne le traitement de surface d'un carbonate de calcium par des composes fluores (H2SiF6 et MgSiF6), en vue d'obtenir des particules opalescentes, resistantes a 1'abrasion et aux acides.  Thus, US Pat. No. 3,179,493 teaches the manufacture of a precipitated calcium carbonate, finely divided and of high purity, by reaction between a calcium salt and a carbonate compound and this, in the presence of a fluoride compound chosen from the fluorides and silicofluorides of potassium, sodium and ammonium. No. 3,793,047 teaches the surface treatment of a calcium carbonate with fluorescent compounds (H 2 SiF 6 and MgSiF 6) in order to obtain opalescent, abrasion-resistant and acid-resistant particles.

D'une part, ces brevets sont tres eloignes de la problematique actuelle de 1'homme du metier, puisque les problemes techniques traites sont tres differents de celui evoque dans le present document. D'autre part, au niveau des solutions mises en oeuvre, les procedes decrits dans ces deux documents different fondamentalement de celui de la presente invention, puisqu'il s'agit d'un procede de fabrication d'un carbonate de calcium (US 3 179 493) et d'un procede de traitement de carbonate de calcium (US 3 793 047). Enfin, les solutions mises en oeuvre dans ces deux documents different egalement de celle de la presente invention, puisqu'elles ne revelent pas la combinaison d'un compose mineral fluore avec un homopolymere de 1'acide acrylique.  On the one hand, these patents are very far removed from the present problem of the skilled person, since the technical problems dealt with are very different from those mentioned in the present document. On the other hand, at the level of the solutions used, the processes described in these two documents differ fundamentally from that of the present invention, since it concerns a process for manufacturing a calcium carbonate (US 3 179,493) and a method for treating calcium carbonate (US 3,793,047). Finally, the solutions implemented in these two documents also differ from that of the present invention, since they do not reveal the combination of a fluorinated mineral compound with a homopolymer of acrylic acid.

Aussi, 1'homme du metier a done mis au point de maniere surprenante une solution nouvelle en vue de disperser dans 1'eau, avec une teneur en poids sec de matiere minerale superieure ou egale A. 65 % en poids de ladite dispersion et une viscosite BrookfieldTM immediate mesuree a 100 tours par minute inferieure a 5 000 mPa.s, des particules minerales telles que notamment du carbonate de calcium, issues du procede de broyage a faible extrait sec sans agent dispersant puis de concentration a haut extrait sec en presence d'agent dispersant.  Also, those skilled in the art have surprisingly developed a novel solution for dispersing in water, with a dry weight content of mineral matter greater than or equal to 65% by weight of said dispersion and a Brookfield ™ instant viscosity measured at 100 rpm less than 5000 mPa.s, mineral particles such as in particular calcium carbonate, resulting from the low solids dry milling process without dispersing agent and high solids concentration concentration in the presence of dispersing agent.

Cette solution repose sur une utilisation d'agents dispersants dans un procede de fabrication d'une dispersion aqueuse de matieres minerales, comprenant les etapes de :  This solution is based on the use of dispersing agents in a process for producing an aqueous dispersion of mineral matter, comprising the steps of:

(a) preparation d'une suspension aqueuse de matiere minerale par broyage desdites matieres minerales sans agent dispersant et / ou agent d'aide au broyage, ladite 7 suspension ayant une concentration en poids sec de matieres minerales inferieure ou egale a 40 % de son poids total,  (a) preparing an aqueous suspension of mineral material by grinding said mineral material without a dispersing agent and / or grinding aid, said suspension having a dry weight concentration of mineral matter of 40% or less; total weight,

(b) concentration de la suspension aqueuse de matieres minerales obtenue au cours de 1'etape a), par des moyens mecaniques et / ou thermiques, en vue d'obtenir une concentration en poids sec de matieres minerales au moins egale A. 65 % du poids total de ladite dispersion,  (b) concentration of the aqueous suspension of mineral matter obtained in step a), by mechanical and / or thermal means, in order to obtain a concentration in dry weight of mineral matter at least equal to A. 65% the total weight of said dispersion,

ou on met en oeuvre :or we implement:

- au moins un agent dispersant introduit entre 1'etape a) et 1'etape b), et / ou pendant 1'etape b), et / ou pendant et apres 1'etape b),  at least one dispersing agent introduced between step a) and step b), and / or during step b), and / or during and after step b),

- sous la forme d'une combinaison : - d'au moins un homopolymere de 1'acide acrylique, - et d'au moins un compose mineral fluore.  in the form of a combination of at least one homopolymer of acrylic acid and at least one fluorinated mineral compound.

Les moyens de concentration mecanique et thermique utilises au cours de 1'etape b) sont choisis parmi ceux bien connus de 1'homme du metier.  The mechanical and thermal concentration means used in step b) are chosen from those well known to those skilled in the art.

L'homme du metier pourra aussi utiliser, au moment de son choix -c'est-a-dire entre 1'etape a) et 1'etape b), et / ou pendant 1'etape b), et / ou pendant et apres 1'etape b)- tout autre agent dispersant de fart anterieur, en vue d'optimiser les caracteristiques de la dispersion finale de matieres minerales qu'il souhaite obtenir. 25 Ainsi, un premier objet de l'invention consiste en des dispersions aqueuses de matieres minerales, caracterisees en ce qu'elles contiennent comme agent dispersant : - au moins un homopolymere de 1'acide acrylique, - et au moins un compose mineral fluore. 30 Ces dispersions aqueuses de matieres minerales sont aussi caracterisees en ce qu'elles possedent une concentration en poids sec de matieres minerales preferentiellement superieure a 68 %, plus preferentiellement superieure a 70 %. Ces dispersions aqueuses de matieres minerales sont aussi caracterisees en ce que les 35 matieres minerales sont choisies parmi le carbonate de calcium naturel ou synthetique, 15 20 les dolomies, le kaolin, le talc, le ciment, le gypse, la chaux, la magnesie, le dioxyde de titane, le blanc satin, le trioxyde d'aluminium ou encore le trihydroxyde d'aluminium, les silices, le mica et le melange de ces charges entre elles, comme les melanges talc-carbonate de calcium, carbonate de calcium-kaolin, ou encore les melanges de carbonate de calcium avec le trihydroxyde d'aluminium ou le trioxyde d'aluminium, ou encore les melanges avec des fibres synthetiques ou naturelles ou encore les co-structures des mineraux comme les co-structures talc-carbonate de calcium ou talcdioxyde de titane, ou leurs melanges. De maniere preferentielle elles sont choisies parmi les carbonates de calcium naturel ou synthetique ou le talc ou le kaolin ou leurs melanges De maniere tres preferentielle elles sont choisies parmi les carbonates de calcium naturel ou synthetique ou leurs melanges.  The skilled person may also use, at the time of his choice-that is, between step a) and step b), and / or during step b), and / or during and after step b) - any other dispersing agent of prior art, in order to optimize the characteristics of the final dispersion of mineral materials that it wishes to obtain. Thus, a first object of the invention consists of aqueous dispersions of mineral matter, characterized in that they contain as dispersing agent: at least one homopolymer of acrylic acid, and at least one fluorinated mineral compound. These aqueous dispersions of mineral matter are also characterized in that they have a concentration in dry weight of mineral matter, preferably greater than 68%, more preferably greater than 70%. These aqueous dispersions of mineral matter are also characterized in that the mineral materials are chosen from natural or synthetic calcium carbonate, dolomites, kaolin, talc, cement, gypsum, lime, magnesia, titanium dioxide, satin white, aluminum trioxide or aluminum trihydroxide, silicas, mica and the mixing of these fillers with each other, such as talc-calcium carbonate mixtures, calcium carbonate-kaolin , or mixtures of calcium carbonate with aluminum trihydroxide or aluminum trioxide, or mixtures with synthetic or natural fibers or the co-structures of minerals such as talc-calcium carbonate co-structures or titanium talcdioxide, or their mixtures. Preferably, they are chosen from natural or synthetic calcium carbonates or talc or kaolin or their mixtures. In a very preferential manner, they are chosen from natural or synthetic calcium carbonates or their mixtures.

Ces dispersions aqueuses de matieres minerales sont aussi caracterisees en ce qu'elles contiennent entre 0,1 % et 3,0 %, preferentiellement entre 0,5 % et 1,5 %, en poids sec par rapport au poids sec de matieres minerales, d'au moins un homopolymere de 1'acide acrylique.  These aqueous dispersions of mineral matter are also characterized in that they contain between 0.1% and 3.0%, preferably between 0.5% and 1.5%, by dry weight relative to the dry weight of mineral matter, at least one homopolymer of acrylic acid.

Ces dispersions aqueuses de matieres minerales sont aussi caracterisees en ce qu'elles contiennent entre 0,01 ,/o et 0,5 %, et preferentiellement entre 0,05 % et 0,25 %, en poids sec par rapport au poids sec de matieres minerales, d'au moins un compose mineral fluor-6.  These aqueous dispersions of mineral matter are also characterized in that they contain between 0.01% and 0.5%, and preferably between 0.05% and 0.25% by dry weight relative to the dry weight of minerals, of at least one fluorine-6 mineral compound.

Ces dispersions aqueuses de matieres minerales sont aussi caracterisees en ce que le compose mineral fluore est choisi parmi les composes NaF, NaHF2, H2SiF6, HKF2, FeF2, PbF2, HNH4F2 et leurs melanges, preferentiellement parmi les composes NaF, H2SiF6, HKF2, et leurs melanges, et en ce qu'il est preferentiellement le compose NaF.  These aqueous dispersions of mineral matter are also characterized in that the fluorinated mineral compound is chosen from the compounds NaF, NaHF 2, H 2 SiF 6, HKF 2, FeF 2, PbF 2, HNH 4 F 2 and their mixtures, preferably from the compounds NaF, H 2 SiF 6, HKF 2, and their mixtures, and in that it is preferentially the compound NaF.

Ces dispersions aqueuses de matieres minerales sont aussi caracterisees en ce que 1'homopolymere de 1'acide acrylique mis en oeuvre est neutralise, totalement ou partiellement, par un agent de neutralisation choisi parmi les hydroxydes et / ou oxydes de calcium, de magnesium, les hydroxydes de sodium, de potassium, ou l'ammoniaque, ou leurs melanges, preferentiellement par un agent de neutralisation choisi parmi l'hydroxyde de sodium, l'ammoniaque, ou leurs melanges, tits preferentiellement par un agent de neutralisation qui est 1'ammoniaque.  These aqueous dispersions of mineral matter are also characterized in that the homopolymer of the acrylic acid employed is neutralized, totally or partially, with a neutralization agent chosen from hydroxides and / or oxides of calcium, magnesium, hydroxides of sodium, potassium, or ammonia, or mixtures thereof, preferably with a neutralizing agent selected from sodium hydroxide, ammonia, or mixtures thereof, preferably with a neutralizing agent which is ammonia .

Ces dispersions aqueuses de matieres mina-ales sont aussi caracterisees en ce 1'homopolymere de 1'acide acrylique mis en oeuvre, possede une masse moleculaire moyenne comprise entre 1 000 et 150 000 Daltons preferentiellement entre 5 000 et 100 000 Daltons et plus preferentiellement entre 15 000 et 80 000 Daltons. Ces dispersions aqueuses de matieres mina-ales sont aussi caracterisees en ce 1'homopolymere de 1'acide acrylique, presente un taux de neutralisation, exprime en pourcentage molaire de sites acides neutralises, compris entre 10 et 100 preferentiellement, entre 50 et 100, et plus preferentiellement entre 70 et 100. 10 Un autre objet de l'invention reside dans l'utilisation de ces dispersions aqueuses dans les domaines de la fabrication de formulations aqueuses contenant des matieres mina-ales, notamment dans le domaine du papier, et plus particulierement dans la fabrication de la feuille de papier et dans la fabrication de sauces de couchage destinees 15 a la production d'une feuille de papier couchee, dans les secteurs du plastique et de la peinture, ainsi que dans la cosmetique et plus particulierement dans la fabrication de pates dentaires.  These aqueous dispersions of mineral materials are also characterized in that the homopolymer of the acrylic acid used, has an average molecular mass of between 1000 and 150 000 Daltons preferably between 5000 and 100 000 Daltons and more preferentially between 15,000 and 80,000 Daltons. These aqueous dispersions of mineral materials are also characterized in that the homopolymer of acrylic acid, has a degree of neutralization, expressed in molar percentage of neutralized acid sites, preferably between 10 and 100, between 50 and 100, and more preferably between 70 and 100. Another object of the invention is in the use of these aqueous dispersions in the fields of the manufacture of aqueous formulations containing mina-ales, especially in the field of paper, and more particularly in the manufacture of the paper sheet and in the manufacture of coating coatings intended for the production of a sheet of coated paper, in the plastics and paint sectors, as well as in cosmetics and more particularly in the manufacture of of toothpastes.

L'exemple suivant illustre l'invention sans pour autant en limiter la portee. 20 25 EXEMPLE 1  The following example illustrates the invention without limiting its scope. EXAMPLE 1

Cet exemple illustre des dispersions aqueuses de matieres mina-ales selon l'invention, preparees a travers les etapes de :  This example illustrates aqueous dispersions of mina-ales according to the invention, prepared through the steps of:

30 (a) preparation d'une suspension aqueuse de carbonate de calcium, qui est un marbre de Norvege dont la granulometrie est telle que 75 % en poids des particules ont un diametre inferieur a 1 m (mesure par un appareil du type SedigraphTM 5100 commercialise par la societe MICROMERITICSTM), par broyage dudit carbonate sans agent d'aide au broyage et sans agent dispersant, a une concentration en poids 35 sec de matieres mina-ales egale a 20 % du poids total de ladite suspension,5 (b) puis concentration de la suspension aqueuse de carbonate de calcium ainsi obtenue au cours de 1'etape a) au moyen d'un evaporateur thermique, en vue d'obtenir une concentration en poids sec de mati&res min&rales la plus &levee possible, oil on a mis en oeuvre, au cours de l'&tape b) :  (A) preparation of an aqueous suspension of calcium carbonate, which is a Norwegian marble whose particle size is such that 75% by weight of the particles have a diameter of less than 1 m (measured by a device of the SedigraphTM 5100 type markets by the company MICROMERITICSTM), by grinding said carbonate without a grinding aid agent and without a dispersing agent, at a dry weight concentration of mina-ales equal to 20% of the total weight of said suspension, (b) then concentration of the aqueous suspension of calcium carbonate thus obtained in step a) by means of a thermal evaporator, in order to obtain the highest dry weight concentration of mineral matter possible, during step b):

soit un agent dispersant selon ]'invention sous la forme d'une combinaison : - d'au moins un homopolym&re de 1'acide acrylique, totalement ou partiellement neutralise, et d'au moins un compose mineral fluor&.  or a dispersing agent according to the invention in the form of a combination of: at least one homopolymer of acrylic acid, totally or partially neutralized, and at least one fluorine mineral compound.

soit un agent dispersant selon fart anterieur.  or a dispersing agent according to the prior art.

Pour chacun des essais n 1 a 17 on a determine pour chaque dispersion aqueuse de matiere mineral& et selon les methodes bien connues de l'homme du metier, la viscosite BrookfieldTM a 100 tours par minute immediatement apr&s 1'etape b), a 25 C, note& loo to  For each of the tests No. 1 to 17, for each aqueous dispersion of mineral material, and according to methods well known to those skilled in the art, the Brookfield ™ viscosity was determined at 100 rpm immediately after step b), at 25 ° C. , note & loo to

Essai n 1 Cet essai illustre ]'invention et met en oeuvre, par rapport au poids sec de carbonate de calcium : - 0,75 % en poids sec d'un homopolymere de 1'acide acrylique dont 70 % en mole des sites acides sont neutralises par 1'hydroxyde de sodium et de poids moleculaire MH, &gal A. 13 300 Daltons, et presentant un indice de viscosite (tel que mesure selon la methode decrite dans le document WO 01 / 048 093) &gal a 0,075, - et 0,10 % en poids sec de fluorure de sodium.  Test No. 1 This test illustrates the invention and uses, relative to the dry weight of calcium carbonate: 0.75% by dry weight of a homopolymer of acrylic acid of which 70 mol% of the acidic sites are neutralized with sodium hydroxide and molecular weight MH, > 13,300 Daltons, and having a viscosity index (as measured by the method described in WO 01/04893) > 0.075, - and 0 10% by dry weight of sodium fluoride.

Essai n 2 Cet essai illustre ]'invention et met en oeuvre, par rapport au poids sec de carbonate de calcium : 0,75 % en poids sec d'un homopolymere de l'acide acrylique totalement neutralise par 1'ammoniaque et de poids moleculaire MW &gal a 10 000 Daltons, et presentant un indice de viscosite (tel que mesure selon la methode decrite dans le document WO 01 / 048 093) &gal A. 0,07, - et 0,10 % en poids sec de fluorure de sodium.  Test No. 2 This test illustrates the invention and uses, relative to the dry weight of calcium carbonate: 0.75% by dry weight of a homopolymer of acrylic acid completely neutralized by ammonia and of molecular weight MW & gal at 10,000 Daltons, and having a viscosity index (as measured by the method described in WO 01/04893) & gal A. 0.07, - and 0.10% by dry weight of sodium fluoride .

Essai n 3 Cet essai illustre l'invention et met en oeuvre, par rapport au poids sec de carbonate de calcium : - 0,75 % en poids sec d'un homopolymere de 1'acide acrylique dont 50 % en mole des sites acides sont neutralises par 1'hydroxyde de sodium et 15 % en mole des sites acides sont neutralises par 1'hydroxyde de magnesium, de poids moleculaire MW egal a 10 000 Daltons, et presentant un indice de viscosite (tel que mesure selon la methode decrite dans le document WO 01 / 048 093) egal a 0,07, - et 0,10 % en poids sec de fluorure de sodium.  Test No. 3 This test illustrates the invention and uses, relative to the dry weight of calcium carbonate: - 0.75% by dry weight of a homopolymer of acrylic acid of which 50 mol% of the acid sites are neutralized with sodium hydroxide and 15 mol% of the acidic sites are neutralized with magnesium hydroxide of molecular weight MW equal to 10,000 Daltons, and having a viscosity number (as measured by the method described in US Pat. WO 01/04893) equal to 0.07, and 0.10% by dry weight of sodium fluoride.

Essai n 4 Cet essai illustre l'invention et met en oeuvre, par rapport au poids sec de carbonate de calcium : - 0,80 % en poids sec d'un homopolymere de 1'acide acrylique dont 40 % en mole des sites acides sont neutralises par 1'hydroxyde de sodium, de poids moleculaire MW egal a 10 000 Daltons, et presentant un indice de viscosite (tel que mesure selon la methode decrite dans le document WO 01 / 048 093) egal a 0,07, et 0,10 % en poids sec de fluorure de sodium.  Test No. 4 This test illustrates the invention and uses, relative to the dry weight of calcium carbonate: - 0.80% by dry weight of a homopolymer of acrylic acid, of which 40 mol% of the acidic sites are neutralized with sodium hydroxide of molecular weight MW equal to 10,000 Daltons and having a viscosity number (as measured by the method described in WO 01/04893) equal to 0.07, and 0, 10% by dry weight of sodium fluoride.

Essai n 5 Cet essai illustre l'invention et met en oeuvre, par rapport au poids sec de carbonate de calcium : 0,70 % en poids sec d'un homopolymere de 1'acide acrylique dont 80 % en mole des sites acides sont neutralises par 1'hydroxyde de sodium et de poids moleculaire MW egal a 10 000 Daltons, et presentant un indice de viscosite (tel que mesure selon la methode decrite dans le document WO 01 / 048 093) egal a 0,07, et 0,10 % en poids sec de fluorure de sodium.  Test No. 5 This test illustrates the invention and uses, relative to the dry weight of calcium carbonate: 0.70% by dry weight of a homopolymer of acrylic acid of which 80 mol% of the acidic sites are neutralized with sodium hydroxide and molecular weight MW equal to 10,000 Daltons, and having a viscosity number (as measured by the method described in WO 01/04893) equal to 0.07, and 0.10 % by dry weight of sodium fluoride.

Essai n 6 Cet essai illustre l'invention et met en ceuvre, par rapport au poids sec de carbonate de calcium : 0,70 % en poids sec d'un homopolymere de 1'acide acrylique dont 60 % en mole des sites acides sont neutralises par 1'hydroxyde de sodium et de poids moleculaire M,,, egal a 10 000 Daltons, et presentant un indice de viscosite (tel que mesure selon la methode decrite dans le document WO 01 / 048 093) egal a 0,07, - et 0,10 % en poids sec de fluorure de sodium.  Test No. 6 This test illustrates the invention and uses, relative to the dry weight of calcium carbonate: 0.70% by dry weight of a homopolymer of acrylic acid of which 60 mol% of the acidic sites are neutralized with sodium hydroxide and molecular weight M ,,, equal to 10,000 Daltons, and having a viscosity number (as measured by the method described in WO 01/04893) equal to 0.07, - and 0.10% by dry weight of sodium fluoride.

Essai n 7 Cet essai illustre l'invention et met en oeuvre, par rapport au poids sec de carbonate de calcium : 0,75 % en poids sec d'un homopolymere de 1'acide acrylique dont 15 % en mole des sites acides sont neutralises par 1'hydroxyde de sodium et de poids moleculaire MW egal a 10 000 Daltons, et presentant un indice de viscosite (tel que mesure scion la methode decrite dans le document WO 01 / 048 093) egal a 0,07, et 0,10 % en poids sec de fluorure de sodium.  Test No. 7 This test illustrates the invention and uses, relative to the dry weight of calcium carbonate: 0.75% by dry weight of a homopolymer of acrylic acid of which 15 mol% of the acidic sites are neutralized with sodium hydroxide and molecular weight MW equal to 10,000 Daltons, and having a viscosity number (as measured by the method described in WO 01/04893) equal to 0.07, and 0.10 % by dry weight of sodium fluoride.

Essai n 8 Cet essai illustre 1'invention et met en ceuvre, par rapport au poids sec de carbonate de calcium : - 0,73 % en poids sec d'un homopolymere de 1'acide acrylique dont 40 % en mole des sites acides sont neutralises par 1'hydroxyde de sodium et de poids moleculaire MW egal a 10 000 Daltons, et presentant un indice de viscosite (tel que mesure selon la methode decrite dans le document WO 01 / 048 093) egal a 0,07, et 0,05 % en poids sec du compose H2SiF6.  Test No. 8 This test illustrates the invention and uses, relative to the dry weight of calcium carbonate: 0.73% by dry weight of a homopolymer of acrylic acid of which 40 mol% of the acid sites are neutralized with sodium hydroxide and molecular weight MW equal to 10,000 Daltons, and having a viscosity number (as measured by the method described in WO 01/04893) equal to 0.07, and 0, 05% by dry weight of the compound H2SiF6.

Essai n 9 Cet essai illustre l'invention et met en oeuvre, par rapport au poids sec de carbonate de calcium : - 0,70 % en poids sec d'un homopolymere de 1'acide acrylique dont 80 % en mole des sites acides sont neutralises par 1'hydroxyde de sodium et de poids moleculaire M, egal a 10 000 Daltons, et presentant un indice de viscosite (tel que mesure selon la methode decrite dans le document WO 01 / 048 093) egal a 0,07, - et 0,25 % en poids sec du compose HKF2.  Test No. 9 This test illustrates the invention and uses, relative to the dry weight of calcium carbonate: - 0.70% by dry weight of a homopolymer of acrylic acid of which 80 mol% of the acidic sites are neutralized with sodium hydroxide and molecular weight M, equal to 10,000 Daltons, and having a viscosity number (as measured by the method described in WO 01/04893) equal to 0.07, - and 0.25% by dry weight of the compound HKF2.

Essai n 10 Cet essai illustre 1'invention et met en oeuvre, par rapport au poids sec de carbonate de calcium : 0,75 % en poids sec d'un homopolymere de l'acide acrylique dont 60 % en mole des sites acides sont neutralises par 1'hydroxyde de sodium et de poids moleculaire M,,, egal a 10 000 Daltons, et presentant un indice de viscosite (tel que mesure selon la methode decrite dans le document WO 01 / 048 093) egal a 0,07, et 0,25 % en poids sec du compose HKF2.  Test No. 10 This test illustrates the invention and uses, relative to the dry weight of calcium carbonate: 0.75% by dry weight of a homopolymer of acrylic acid of which 60 mol% of the acidic sites are neutralized with sodium hydroxide and a molecular weight M ,,, equal to 10,000 Daltons, and having a viscosity index (as measured by the method described in WO 01/04893) equal to 0.07, and 0.25% by dry weight of the compound HKF2.

Essai n 11 Cet essai illustre l'invention et met en oeuvre, par rapport au poids sec de carbonate de calcium : - 0,70 % en poids sec d'un homopolymere de 1'acide acrylique dont 80 % en mole des sites acides sont neutralises par 1'hydroxyde de sodium et de poids moleculaire MW egal a 10 000 Daltons, et presentant un indice de viscosite (tel que mesure selon la methode decrite dans le document WO 01 / 048 093) egal a 0,07, et 0,25 % en poids sec du compose FeF2.  Test No. 11 This test illustrates the invention and uses, relative to the dry weight of calcium carbonate: - 0.70% by dry weight of a homopolymer of acrylic acid of which 80 mol% of the acid sites are neutralized with sodium hydroxide and molecular weight MW equal to 10,000 Daltons, and having a viscosity number (as measured by the method described in WO 01/04893) equal to 0.07, and 0, 25% by dry weight of the compound FeF2.

Essai n 12 Cet essai illustre 1'invention et met en oeuvre, par rapport au poids sec de carbonate de calcium : - 0,70 % en poids sec d'un homopolymere de 1'acide acrylique dont 80 % en mole des sites acides sont neutralises par 1'hydroxyde de sodium et de poids moleculaire M,,, egal a 10 000 Daltons, et presentant un indice de viscosite (tel que mesure selon la methode decrite dans le document WO 01 / 048 093) egal a 0,07, - et 0,25 % en poids sec du compose PbF2.  Test No. 12 This test illustrates the invention and uses, relative to the dry weight of calcium carbonate: - 0.70% by dry weight of a homopolymer of acrylic acid of which 80 mol% of the acidic sites are neutralized with sodium hydroxide and with a molecular weight M ,,, equal to 10,000 Daltons, and having a viscosity number (as measured by the method described in WO 01/04893) equal to 0.07, and 0.25% by dry weight of the compound PbF2.

Essai n 13 14 Cet essai illustre 1'invention et met en oeuvre, par rapport au poids sec de carbonate de calcium : - 0,70 % en poids sec d'un homopolymere de 1'acide acrylique dont 40 % en mole des sites acides sont neutralises par 1'hydroxyde de sodium et de poids moleculaire MW egal a 10 000 Daltons, et presentant un indice de viscosite (tel que mesure selon la methode decrite dans le document WO 01 / 048 093) egal a 0,07, et 0,25 % en poids sec du compose HNH4F2.  Test No. 13 This test illustrates the invention and uses, relative to the dry weight of calcium carbonate: 0.70% by dry weight of a homopolymer of acrylic acid, of which 40 mol% of the acidic sites are neutralized with sodium hydroxide and molecular weight MW equal to 10,000 Daltons, and having a viscosity number (as measured by the method described in WO 01/04893) equal to 0.07, and 0 25% by dry weight of the compound HNH4F2.

Essai n 14 Cet essai illustre l'invention et met en oeuvre, par rapport au poids sec de carbonate de calcium : 0,75 % en poids sec d'un homopolymere de 1'acide acrylique totalement neutralise par 1'hydroxyde de sodium et de poids moleculaire MW egal a 50 000 Daltons, et ayant un indice de viscosite egal a 0,8 (tel que mesure selon la methode decrite dans le document WO 01 / 048 093), et 0,10 % en poids sec de fluorure de sodium.  Test No. 14 This test illustrates the invention and uses, relative to the dry weight of calcium carbonate: 0.75% by dry weight of a homopolymer of acrylic acid completely neutralized with sodium hydroxide and sodium hydroxide. MW molecular weight equal to 50,000 Daltons, and having a viscosity number equal to 0.8 (as measured by the method described in WO 01/04893), and 0.10% by dry weight of sodium fluoride .

Essai n 15 Cet essai illustre l'invention et met en oeuvre, par rapport au poids sec de carbonate de calcium : - 0,75 % en poids sec d'un homopolymere de 1'acide acrylique totalement neutralise par 1'hydroxyde de potassium et de poids moleculaire M,,, egal a 50 000 Daltons, et ayant un indice de viscosite egal a 0,8 (tel que mesure selon la methode decrite dans le document WO 01 / 048 093), et 0,10 % en poids sec de fluorure de sodium.  Test No. 15 This test illustrates the invention and uses, relative to the dry weight of calcium carbonate: - 0.75% by dry weight of a homopolymer of acrylic acid completely neutralized with potassium hydroxide and of molecular weight M ,,, equal to 50,000 Daltons, and having a viscosity number equal to 0.8 (as measured by the method described in WO 01/04893), and 0.10% by dry weight. sodium fluoride.

Essai n 16 Cet essai illustre l'invention et met en oeuvre, par rapport au poids sec de carbonate de calcium : 0,75 % en poids sec d'un homopolymere de 1'acide acrylique dont 50 % en mole des sites acides sont neutralises par 1'hydroxyde de magnesium et 30 % en mole des sites acides sont neutralises par 1'hydroxyde de sodium, et de poids moleculaire MW egal a 50 000 Daltons, et ayant un indice de viscosite egal a 0,8 (tel que mesure selon la methode decrite dans le document WO 01 / 048 093), - et 0,10 % en poids sec de fluorure de sodium.  Test No. 16 This test illustrates the invention and uses, relative to the dry weight of calcium carbonate: 0.75% by dry weight of a homopolymer of acrylic acid of which 50 mol% of the acidic sites are neutralized with magnesium hydroxide and 30 mol% of the acidic sites are neutralized with sodium hydroxide, and MW of 50,000 Daltons, and having a viscosity number of 0.8 (as measured by the method described in WO 01/048 093), and 0.10% by dry weight of sodium fluoride.

Essai n 17 Cet essai illustre 1'invention et met en oeuvre, par rapport au poids sec de carbonate de calcium : - 0,75 % en poids sec d'un homopolymere de 1'acide acrylique dont 80 % en mole des sites acides sont neutralises par 1'hydroxyde de sodium et de poids moleculaire M, egal a 50 000 Daltons, et ayant un indice de viscosite egal a 0,8 (tel que mesure selon la methode decrite dans le document WO 01 / 048 093), - et 0,10 % en poids sec de fluorure de sodium.  Test No. 17 This test illustrates the invention and uses, relative to the dry weight of calcium carbonate: - 0.75% by dry weight of a homopolymer of acrylic acid of which 80 mol% of the acidic sites are neutralized with sodium hydroxide and molecular weight M, equal to 50,000 Daltons, and having a viscosity number equal to 0.8 (as measured by the method described in WO 01/04893), - and 0.10% by dry weight of sodium fluoride.

Pour chacun des essais n 1 a 17, les valeurs de la viscosite BrookfieldTMmesuree a t=0, a 25 C, et a une vitesse de rotation de 100 tours / minute (en mPa.$) notee loo to, et les valeurs de 1'extrait sec (en pourcentage en poids sec de matiere minerale par rapport au poids totale de la dispersion obtenue) note ES, sont indiquees dans le tableau 1. dispersant no homopolymere de 1'acide acrylique compose dispersion essai fluore agent taux poids quantite2 nature quantite 100t0 ES (%) neut. neut.' moleculaire (%) (%) (mPa.$) (%) (Daltons) 1 NaOH 70 13 300 0,75 NaF 0,10 860 71,3 2 NH3 100 10 000 0,75 NaF _ _ 71,5 0,10 140 3 NaOH 50 10 000 0,75 NaF _ _ _ Mg(OH)2 15 0,10 1340 65,4 4 NaOH 40 10 000 0,80 NaF 0,10 4 900 68,3 _ NaOH 80 10 000 0,70 NaF 0,10 2240 _ 65,8 _ 6 NaOH 60 10 000 0,70 _ NaF 0,10 2420 70,0 _ 7 NaOH 15 10 000 0,75 NaF 0,10 245 70, 1 8 NaOH 40 10 000 0,73 H2SiF6 0,05 2470 66,0 9 NaOH 80 10 000 0,70 HKF2 0,25 2460 66,5 NaOH 60 10 000 0,75 HKF2 0,25 2410 65,4 11 NaOH _ 10 000 0,70 FeF2 0,25 1500 71,0 80 12 _ 80 10 000 0,70 PbF2 0,25 2450 65,5 _ NaOH 13 NaOH 40 10 000 0,70 HNH4F2 0,25 3 290 65,5 14 NaOH 100 50 000 0,75 NaF 0,10 245 _ 70,1 _ _ _ KOH 100 50 000 0,75 NaF 0,10 555 70,7 16 Mg(OH)2 50 0,75 NaF 0,10 860 70,0 NaOH 30 50 000 17 NaOH 80 50 000 0,75 NaF 0,10 620 71,1 Tableau 1 : caracteristiques des dispersants selon l'invention et valeurs de ES et loo to pour les dispersions obtenues selon l'invention. Dans ce tableau :  For each of the tests Nos. 1 to 17, the values of the Brookfield ™ viscosity at t = 0, at 25 ° C., and a rotational speed of 100 rpm (in mPa · s), noted at 100 ° C, and the values of 1 dry extract (in percentage by dry weight of mineral matter with respect to the total weight of the dispersion obtained) note ES, are indicated in Table 1. dispersant no homopolymer of acrylic acid compound dispersion test fluorine agent rate weight quantite2 nature quantity 100t0 ES (%) neut. neut. ' Molecular (%) (%) (mPa. $) (%) (Daltons) 1 NaOH 70 13 300 0.75 NaF 0.10 860 71.3 2 NH3 100 10,000 0.75 NaF _ 71.5 0, 10 140 3 NaOH 50 10,000 0.75 NaF Mg (OH) 2 0.10 1340 65.4 4 NaOH 40 10,000 0.80 NaF 0.10 4 900 68.3 NaOH 80 10,000 0 70 NaF 0.10 2240 65.8 6 NaOH 60 10,000 0.70 NaF 0.10 2420 70.0 7 NaOH 10,000 0.75 NaF 0.10 245 70, 18 NaOH 40 10 000 0.73 H2SiF6 0.05 2470 66.0 9 NaOH 80 10,000 0.70 HKF2 0.25 2460 66.5 NaOH 60 10,000 0.75 HKF2 0.25 2410 65.4 11 NaOH-10,000 0, 70 FeF2 0.25 1500 71.0 80 12 _ 80 10 000 0.70 PbF2 0.25 2450 65.5 _ NaOH 13 NaOH 40 10,000 0.70 HNH4F2 0.25 3 290 65.5 14 NaOH 100 50 000 0.75 NaF 0.10 245 _ 70.1 _ _ _ KOH 100 50 000 0.75 NaF 0.10 555 70.7 16 Mg (OH) 2 50 0.75 NaF 0.10 860 70.0 NaOH 50 000 17 NaOH 80 50 000 0.75 NaF 0.10 620 71.1 TABLE 1 Characteristics of the dispersants according to the invention and ES values and 100% for the dispersions obtained according to the invention. In this table :

taux neut. 1 (%) designe le taux de neutralisation de chaque homopolymere, exprime en pourcentage molaire de sites acides neutralises, 10 quantite2 designe la quantite d'homopolymere utilise, exprimee en pourcentage en poids sec dudit polymere par rapport au poids sec total de matieres minerales, - quantite3 designe la quantite de compose mineral fluore utilise, exprimee en pourcentage en poids sec dudit compose mineral fluore par rapport au poids sec total de matieres minerales, 15 11100 to designe la viscosite BrookfieldTM mesuree a 100 tours par minute immediatement apres 1'etape b), et notee !Iwo t0~ ES designe 1'extrait sec exprime en pourcentage en poids sec de matieres minerales par rapport au poids total de chaque dispersion. 5 La lecture du tableau 1 demontre done que les dispersions aqueuses de matieres minerales selon 1'invention possedent des concentrations en poids sec de matieres mina-ales superieures a 65 % de leurs poids total, et ont pu etre obtenues a partir de suspensions initiales de carbonate de calcium qui avaient ete broyees sans agent dispersant ni agent d'aide au broyage a une concentration en matiere seche inferieure a 40 % du poids total de ladite suspension.  Neutral rate. 1 (%) denotes the degree of neutralization of each homopolymer, expressed as a molar percentage of neutralized acidic sites, where quantity refers to the amount of homopolymer used, expressed as a percentage by dry weight of said polymer relative to the total dry weight of mineral matter, quantity refers to the amount of fluorinated mineral compound used, expressed as a percentage by dry weight of said fluorinated mineral compound relative to the total dry weight of mineral matter, 11100 to designate the Brookfield ™ viscosity measured at 100 rpm immediately after step b ), and noted! Iwo t0 ~ ES designates the dry extract expressed as a percentage by dry weight of mineral matter with respect to the total weight of each dispersion. The reading of Table 1 thus shows that the aqueous dispersions of mineral matter according to the invention have dry weight concentrations of mina-ales greater than 65% of their total weight, and could be obtained from initial suspensions of calcium carbonate which had been milled without a dispersing agent or grinding aid agent has a dry matter concentration of less than 40% of the total weight of said suspension.

De maniere encore plus avantageuse, ce tableau demontre qu'on peut obtenir des dispersions aqueuses de matieres mina-ales selon l'invention avec des concentrations en poids sec de matieres mina-ales superieures a 65 %, et une viscosite BrookfieldTM immediate mesuree a 100 tours par minute inferieure a 5 000 mPa.s.  Even more advantageously, this table shows that aqueous dispersions of mina-ales according to the invention can be obtained with dry weight concentrations of mina-ales greater than 65%, and an instant BrookfieldTM viscosite measured at 100.degree. revolutions per minute less than 5,000 mPa.s.

Pour certains essais, on obtient meme de maniere surprenante des concentrations en poids sec de matieres minerales superieures a 70 %, et une viscosite BrookfieldTM immediate mesuree a 100 tours par minute inferieure a 500 mPa.s (cas des essais n 2, 7 et 14).  For some tests, concentrations in dry weight of mineral matter greater than 70% are surprisingly obtained, and an instant BrookfieldTM viscosite measured at 100 revolutions per minute of less than 500 mPa · s (case of tests Nos. 2, 7 and 14). ).

De tels resultats repondent parfaitement a la demande de 1'homme du metier.  Such results perfectly correspond to the demand of the person skilled in the art.

Essai n 18 Cet essai illustre fart anterieur et met en oeuvre 0,75 % en poids sec, par rapport au poids sec de carbonate de calcium, d'un homopolymere de 1'acide acrylique totalement neutralise par 1'hydroxyde de sodium et de poids moleculaire egal a 14 000 Daltons.  Test No. 18 This experiment illustrates the prior art and employs 0.75% by dry weight, based on the dry weight of calcium carbonate, of a homopolymer of acrylic acid completely neutralized with sodium hydroxide and weight. molecular weight equal to 14,000 Dalton.

Essai n 19 Cet essai illustre fart anterieur et met en oeuvre 0,75 % en poids sec, par rapport au poids sec de carbonate de calcium, d'un homopolymere de 1'acide acrylique totalement neutralise par 1'hydroxyde de sodium et de poids moleculaire egal a 12 000 Daltons.  Test No. 19 This experiment illustrates the prior art and employs 0.75% by dry weight, based on the dry weight of calcium carbonate, of a homopolymer of acrylic acid completely neutralized with sodium hydroxide and weight. molecular weight equal to 12 000 Daltons.

Essai n 20 Cet essai illustre fart anterieur et met en oeuvre 0,75 % en poids sec, par rapport au poids sec de carbonate de calcium, d'un homopolymere de 1'acide acrylique totalement neutralise par 1'ammoniaque et de poids moleculaire egal a 10 000 Daltons.  Test No. 20 This experiment illustrates the prior art and employs 0.75% by dry weight, based on the dry weight of calcium carbonate, of a homopolymer of acrylic acid completely neutralized by ammonia and of equal molecular weight. has 10,000 Daltons.

Essai n 21 Cet essai illustre fart anterieur et met en oeuvre 0,80 % en poids sec, par rapport au poids sec de carbonate de calcium, d'un homopolymere de 1'acide acrylique totalement neutralise par 1'ammoniaque et de poids moleculaire egal a 10 000 Daltons.  Test No. 21 This test illustrates the prior art and employs 0.80% by dry weight, based on the dry weight of calcium carbonate, of a homopolymer of acrylic acid completely neutralized by ammonia and of equal molecular weight. has 10,000 Daltons.

Essai n 22 Cet essai illustre fart anterieur et met en oeuvre 0,85 % en poids sec, par rapport au poids sec de carbonate de calcium, d'un homopolymere de 1'acide acrylique totalement neutralise par 1'ammoniaque et de poids moleculaire egal a 10 000 Daltons.  Test No. 22 This experiment illustrates the prior art and employs 0.85% by dry weight, based on the dry weight of calcium carbonate, of a homopolymer of acrylic acid completely neutralized by ammonia and of equal molecular weight. has 10,000 Daltons.

Pour chacun des essais n 18 a 22, les valeurs de la viscosite BrookfieldTM mesuree a t=0, a 25 C, et a une vitesse de rotation de 100 tours / minute (en mPa.$) not& 11100 et les valeurs de 1'extrait sec (en pourcentage en poids sec de matiere minerale par rapport au poids totale de la dispersion obtenue) note ES, sont indiquees dans le tableau 2. n Dispersant Dispersion essai (homopolymere de l'acide acrylique) agent taux poids quantite2 loo to ES neut. neut.' moleculaire (%) (mPa.$) (%) (%) (Daltons) 18 NaOH 100 14 000 0,75 9 200 65,9 19 NaOH 100 12 000 0,75 5 500 64,9 20 NH; 100 10 000 0,75 5 600 40,0 _ 21 NH1100 10 000 0,80 5 500 45,1 22 NH1100 10 000 0,85 6 230 55,2 Tableau 2 : caracteristiques des dispersants selon fart anterieur et valeurs de ES et loo to pour les dispersions obtenues.  For each of tests Nos. 18 to 22, the values of the Brookfield ™ viscosity measured at t = 0, at 25 ° C, and at a rotational speed of 100 rpm (in mPa · s) are 11100 and the values of the dry extract (in percentage by dry weight of mineral matter relative to the total weight of the dispersion obtained) note ES, are indicated in table 2. n Dispersant Dispersion test (homopolymer of acrylic acid) agent rate weight quantity2 loo to ES neut. neut. ' Molecular (%) (mPa. $) (%) (%) (Daltons) 18 NaOH 100 14,000 0.75 9 200 65.9 19 NaOH 100 12,000 0.75 5,500 64.9 NH; 100 10 000 0.75 5 600 40.0 _ 21 NH1100 10 000 0.80 5 500 45.1 22 NH1100 10 000 0.85 6 230 55.2 Table 2: Characteristics of dispersants according to prior art and ES values and loo to for the dispersions obtained.

Dans ce tableau : 20 - taux neut.1 (%) designe le taux de neutralisation de chaque homopolymere, exprime en pourcentage molaire de sites acides neutralises, - quantite2 designe la quantite d'homopolymere utilise, exprimee en pourcentage en poids sec dudit polymere par rapport au poids sec total de matieres minerales, limo t0 designe la viscosite BrookfieldTM mesuree a 100 tours par minute 25 immediatement apres 1'etape b), et notee loo to, ES designe 1'extrait sec exprime en pourcentage en poids sec de matieres minerales par rapport au poids total de chaque dispersion.15 19 La lecture du tableau 2 demontre qu'aucun des essais n 18 a 22 ne permet d'obtenir une viscosite Brookfield -mesuree A. 100 tours par minute immediatement apt-es 1'etape b)- inferieure a 5 000 mPa.s et a la fois un extrait sec superieur a 65 % en poids de matieres minerales : ceci reste pourtant l'objectif principal de 1'homme du metier a travers le probleme technique que cherche a resoudre la presente Demande.  In this table: Neutral level (%) denotes the degree of neutralization of each homopolymer, expressed as a molar percentage of neutralized acid sites. Quantite2 is the amount of homopolymer used, expressed as a percentage by dry weight of said polymer by relative to the total dry weight of mineral matter, limo t0 is BrookfieldTM viscosite measured at 100 rpm immediately after step b), and noting 100%, ES means dry extract expressed as a percentage by dry weight of mineral matter relative to the total weight of each dispersion. 15 19 The reading of Table 2 shows that none of the tests Nos. 18 to 22 makes it possible to obtain a Brookfield viscosite -measures A. 100 rpm immediately apt in step b ) - less than 5000 mPa.s and at the same time a dry extract greater than 65% by weight of mineral matter: this remains however the main objective of the man of the trade through the technical problem that seeks to solve this presents Request.

La comparaison avec les resultats figurant dans le tableau 1 demontre donc 1'effet surprenant obtenu avec les dispersions aqueuses selon l'invention.  The comparison with the results given in Table 1 thus demonstrates the surprising effect obtained with the aqueous dispersions according to the invention.

Enfin, on a realise un essai mettant en oeuvre un copolymere de 1'acide acrylique et de 1'anhydride maleique tel que decrit dans le document EP 0 850 685 (essai n 23), et un essai mettant en oeuvre un homopolymere de 1'acide acrylique tel que decrit dans le document WO 01 / 048 093 (essai n 24) : ces deux essais illustrent fart anterieur, et mettent en oeuvre lesdits polymeres dans le mane procede que celui decrit pour les essais n 1 a 17.  Finally, an experiment was carried out employing a copolymer of acrylic acid and maleic anhydride as described in EP 0 850 685 (test No. 23), and a test using a homopolymer of 1 '. acrylic acid as described in WO 01/04893 (test No. 24): these two tests illustrate the prior art, and implement said polymers in the mane method as that described for tests No. 1 to 17.

Essai n 23 Cet essai illustre fart anterieur et met en oeuvre, par rapport au poids sec de carbonate de calcium 0,75 % en poids sec d'un copolymere de 1'acide acrylique et de 1'anhydride maleique (dans un melange molaire 3 :1) totalement neutralise par la soude, et de poids moleculaire MW egal a 22 500 Daltons.  Test No. 23 This experiment illustrates the prior art and employs, based on the dry weight of calcium carbonate, 0.75% by dry weight of a copolymer of acrylic acid and maleic anhydride (in a molar mixture). : 1) completely neutralized by sodium hydroxide, and of molecular weight MW equal to 22,500 Daltons.

Essai n 24 Cet essai illustre fart anterieur et met en oeuvre, par rapport au poids sec de carbonate de calcium 0,75 % en poids sec d'un homopolymere de 1'acide acrylique totalement neutralise par la soude, et de poids moleculaire MW egal a 50 000 Daltons, et presentant un indice de viscosite (tel que mesure selon la methode decrite dans le document WO 01 / 048 093) egal A. 0,8.  Test No. 24 This test illustrates the prior art and uses, relative to the dry weight of calcium carbonate, 0.75% by dry weight of a homopolymer of acrylic acid completely neutralized by sodium hydroxide, and of MW equal molecular weight. at 50,000 Daltons, and having a viscosity index (as measured by the method described in WO 01/04893) equal to 0.8.

Pour chacun des essais n 23 et 24, les valeurs de la viscosite BrookfieldTM mesurees a t = 0, A. 25 C, et a une vitesse de rotation de 100 tours / minute (en mPa.$) notee loo to, et les valeurs de 1'extrait sec (en pourcentage en poids sec de matiere minerale par rapport au poids totale de la dispersion obtenue) note ES, sont indiquees dans le tableau 3.35 On a egalement reporte dans le tableau 3 les resultats obtenus pour les essais n 2, 7 et 14. dispersant dispersion no invention compose to ES (%) essai / fluore too art anterieur (mPa.$) nature agent taux poids quantite2 quantite3 neut. neut.' moleculaire (%) (%) (Daltons) nature (%) 23 art anterieur copolymere NaOH 100 22 500 0,75 - - 260 70,1 24 art anterieur homopolymere NaOH 100 50 000 0,75 - - 5 270 71,8 2 invention homopolymere NH3 100 10 000 0,75 NaF 0,1 140 71,5 7 invention homopolymere NaOH 15 10 000 0,75 NaF 0,1 245 70,1 14 invention homopolymere NaOH 100 50 000 0,75 NaF 0,1 245 70,1 Tableau 3 : caracteristiques des dispersants selon l'invention et valeurs de ES et l00 t0 pour les dispersions obtenues selon 1'invention.  For each of tests 23 and 24, the Brookfield ™ viscosite values measured at t = 0, A. 25 C, and had a rotational speed of 100 rpm (in mPa. of the dry extract (in percentage by dry weight of mineral matter relative to the total weight of the dispersion obtained) note ES, are indicated in table 3.35 Table 3 also gives the results obtained for tests n 2, 7 and 14. Dispersant Dispersant No. Composed to ES (%) Test / Fluoride Too Far Prior Art (mPa. $) Nature Agent Rate Weight Quantite2 Quantite3 Neut. neut. ' Molecular (%) (%) (Daltons) Nature (%) 23 Prior art Copolymer NaOH 100 22 500 0.75 - - 260 70.1 24 Prior art Homopolymer NaOH 100 50 000 0.75 - - 5 270 71.8 2 homopolymer NH3 100 10,000 0.75 NaF 0.1 140 71.5 7 homopolymer homopolymer NaOH 10 000 0.75 NaF 0.1 245 70.1 14 homopolymer invention NaOH 100 50 000 0.75 NaF 0.1 245 70.1 Table 3: Characteristics of the dispersants according to the invention and ES values and 100% for the dispersions obtained according to the invention.

Dans ce tableau :In this table :

- le terme homopolymere designe un homopolymere de 1'acide acrylique, - le terme copolymere designe un copolymere de 1'acide acrylique et de 1'anhydride maleique (dans un melange molaire 3 :1) et de poids moleculaire 22 500 Daltons, - taux neut. 1 (%) designe le taux de neutralisation de chaque homopolymere ou copolymere, exprime en pourcentage molaire de sites acides neutralises, quantite2 designe la quantite d'homopolymere ou de copolymere utilise, exprimee en pourcentage en poids sec dudit polymere par rapport au poids sec total de matieres minerales, - quantite3 designe la quantite de compose mineral fluor& utilise, exprimee en pourcentage en poids sec dudit compose mineral fluor& par rapport au poids sec total de matieres minerales, - loo to designe la viscosite BrookfieldTM mesuree a 100 tours par minute immediatement apres 1'etape b), et note& too toy - ES designe 1'extrait sec exprime en pourcentage en poids sec de matieres minerales par rapport au poids total de chaque dispersion.  the term homopolymer denotes a homopolymer of acrylic acid; the term copolymer refers to a copolymer of acrylic acid and maleic anhydride (in a 3: 1 molar mixture) and of molecular weight 22,500 Daltons; neut. 1 (%) denotes the degree of neutralization of each homopolymer or copolymer, expressed in molar percentage of neutralized acidic sites, quantity2 refers to the amount of homopolymer or copolymer used, expressed as a percentage by dry weight of said polymer relative to the total dry weight of mineral matter, - quantity means the quantity of mineral fluoride compound used, expressed as a percentage by dry weight of the said fluorine-mineral compound, relative to the total dry weight of mineral matter, - 100 per cent means the Brookfield ™ viscosity measured at 100 revolutions per minute immediately after Step b), and note & too toy - ES means dry extract expressed as a percentage by dry weight of mineral matter based on the total weight of each dispersion.

Ces resultats demontrent que les dispersions aqueuses de matieres minerales selon l'invention, apres optimisation de celles-ci, fournissent a 1'homme du metier des solutions encore plus performantes que celles consistant dans les selections tres restrictives proposees dans les deux seuls documents de 1'etat de la technique, alors accessibles a lui pour resoudre son probleme (WO 01 / 048 093 et EP 0 850 685). 2225  These results show that the aqueous dispersions of mineral matter according to the invention, after optimization of these, provide to the person skilled in the art even more effective solutions than those consisting of the very restrictive selections proposed in the two only documents of the invention. state of the art, then available to him to solve his problem (WO 01/048 093 and EP 0 850 685). 2225

Claims (19)

REVENDICATIONS 1 - Dispersions aqueuses de matieres minerales, caracterisees en ce qu'elles contiennent comme agent dispersant : au moins un homopolymere de 1'acide acrylique, - et au moins un compose mineral fluore.  1 - Aqueous dispersions of mineral matter, characterized in that they contain as dispersing agent: at least one homopolymer of acrylic acid, and at least one fluorinated mineral compound. 2 - Dispersions aqueuses de matieres minerales selon la revendication 1, caracterisees en ce qu'elle possedent une concentration en poids sec de matieres minerales preferentiellement superieure a 68 %, plus preferentiellement superieure a 70 %.  2 - Aqueous dispersions of mineral matter according to claim 1, characterized in that it has a dry weight concentration of mineral matter preferably greater than 68%, more preferably greater than 70%. 3 - Dispersions aqueuses de matieres minerales selon rune des revendications 1 ou 2, caracterisees en ce que les matieres minerales sont choisies parmi le carbonate de calcium naturel ou synthetique, les dolomies, le kaolin, le talc, le ciment, le gypse, la chaux, la magnesie, le dioxyde de titane, le blanc satin, le trioxyde d'aluminium ou encore le trihydroxyde d'aluminium, les silices, le mica et le melange de ces charges entre elles, comme les melanges talc-carbonate de calcium, carbonate de calcium-kaolin, ou encore les melanges de carbonate de calcium avec le trihydroxyde d'aluminium ou le trioxyde d'aluminium, ou encore les melanges avec des fibres synthetiques ou naturelles ou encore les co-structures des mineraux comme les co-structures talc-carbonate de calcium ou talc-dioxyde de titane, ou leurs melanges.  3 - Aqueous dispersions of mineral matter according to one of claims 1 or 2, characterized in that the mineral materials are selected from natural or synthetic calcium carbonate, dolomites, kaolin, talc, cement, gypsum, lime , magnesia, titanium dioxide, satin white, aluminum trioxide or aluminum trihydroxide, silicas, mica and the mixing of these fillers with one another, such as talc-calcium carbonate mixtures, carbonate of calcium-kaolin, or mixtures of calcium carbonate with aluminum trihydroxide or aluminum trioxide, or mixtures with synthetic or natural fibers or the co-structures of minerals such as talc co-structures calcium carbonate or talc-titanium dioxide, or mixtures thereof. 4 - Dispersions aqueuses de matieres minerales selon la revendication 3, caracterisees en ce que les matieres minerales sont choisies parmi les carbonates de calcium naturel ou synthetique ou le talc ou le kaolin ou leurs melanges.  4 - Aqueous dispersions of mineral matter according to claim 3, characterized in that the mineral materials are selected from natural or synthetic calcium carbonates or talc or kaolin or mixtures thereof. 5 - Dispersions aqueuses de matieres minerales selon la revendication 4, caracterisees en ce que les matieres minerales sont choisies parmi les carbonates de calcium naturel ou synthetique ou leurs melanges.  5 - Aqueous dispersions of mineral matter according to claim 4, characterized in that the mineral materials are selected from natural or synthetic calcium carbonates or mixtures thereof. 6 - Dispersions aqueuses de matieres minerales selon rune des revendications 1 a 5, caracterisees en ce qu'elles contiennent entre 0,1 % et 3,0 %, preferentiellement entre 0,5 % et 1,5 %, en poids sec par rapport au poids sec de matieres minerales, d'au moins un homopolymere de 1'acide acrylique. 35 524  6 - Aqueous dispersions of mineral matter according to one of claims 1 to 5, characterized in that they contain between 0.1% and 3.0%, preferably between 0.5% and 1.5%, by dry weight relative to to the dry weight of mineral matter, at least one homopolymer of acrylic acid. 35,524 7 - Dispersions aqueuses de matieres minerales selon 1'une des revendications 1 a 6, caracterisees en ce qu'elles contiennent entre 0,01 % et 0,5 %, et preferentiellement entre 0,05 % et 0,25 %, en poids sec par rapport au poids sec de matieres minerales, d'au moins un compose mineral fluore.  7 - Aqueous dispersions of mineral matter according to one of claims 1 to 6, characterized in that they contain between 0.01% and 0.5%, and preferably between 0.05% and 0.25%, by weight dry with respect to the dry weight of mineral matter, of at least one fluorinated mineral compound. 8 - Dispersions aqueuses de matieres minerales selon rune des revendications 1 A. 7, caracterisees en ce que le compose mineral fluore est choisi parmi les composes NaF, NaHF2, H2SiF6, HKF2, FeF2, PbF2, HNH4F2 et leurs melanges. 10  8 - Aqueous dispersions of mineral matter according to one of claims 1 A. 7, characterized in that the mineral fluoride compound is selected from the compounds NaF, NaHF2, H2SiF6, HKF2, FeF2, PbF2, HNH4F2 and mixtures thereof. 10 9 - Dispersions aqueuses de matieres minerales selon la revendication 8, caracterisees en ce que le compose mineral fluore est choisi parmi les composes NaF, H2SiF6, HKF2, et leurs melanges.  9 - Aqueous dispersions of mineral matter according to claim 8, characterized in that the mineral fluoride compound is selected from the compounds NaF, H2SiF6, HKF2, and mixtures thereof. 10 - Dispersions aqueuses de matieres minerales selon la revendication 9, caracterisees 15 en ce que le compose mineral fluore est le compose NaF.  10 - Aqueous dispersions of mineral matter according to claim 9, characterized in that the mineral fluoride compound is the compound NaF. 11 - Dispersions aqueuses de matieres minerales selon 1'une des revendications 1 a 10, caracterisees en ce que 1'homopolymere de 1'acide acrylique mis en oeuvre est neutralise, totalement ou partiellement, par un agent de neutralisation choisi parmi les 20 hydroxydes et / ou oxydes de calcium, de magnesium, les hydroxydes de sodium, de potassium, ou l'ammoniaque, ou leurs melanges.  11 - Aqueous dispersions of mineral matter according to one of claims 1 to 10, characterized in that the homopolymer of the acrylic acid used is neutralized, totally or partially, with a neutralizing agent chosen from hydroxides and / or oxides of calcium, magnesium, hydroxides of sodium, potassium, or ammonia, or mixtures thereof. 12 - Dispersions aqueuses de matieres minerales selon la revendication 11, caracterisees en ce que 1'agent de neutralisation est choisi parmi 1'hydroxyde de sodium, 25 1'ammoniaque, ou leurs melanges.  12. Aqueous dispersions of mineral matter according to claim 11, characterized in that the neutralizing agent is selected from sodium hydroxide, ammonia, or mixtures thereof. 13 - Dispersions aqueuses de matieres minerales selon la revendication 12, caracterisees en ce que l'agent de neutralisation est l'ammoniaque. 30  13 - Aqueous dispersions of mineral matter according to claim 12, characterized in that the neutralizing agent is ammonia. 30 14 - Dispersions aqueuses de matieres minerales selon rune des revendications 1 a 13, caracterisees en ce que 1'homopolymere de 1'acide acrylique mis en oeuvre, possede une masse moleculaire moyenne comprise entre 1 000 et 150 000 Daltons.  14 - Aqueous dispersions of mineral matter according to one of claims 1 to 13, characterized in that the homopolymer of the acrylic acid used, has a mean molecular mass of between 1000 and 150 000 Daltons. 15 - Dispersions aqueuses de matieres minerales selon la revendication 14, caracterisees 25 en ce 1'homopolymere de 1'acide acrylique mis en oeuvre, possede une masse moleculaire moyenne comprise entre 5 000 et 100 000 Daltons.  Aqueous dispersions of mineral matter according to claim 14, characterized in that the homopolymer of the acrylic acid employed, has an average molecular weight of between 5,000 and 100,000 Daltons. 16 - Dispersions aqueuses de matieres minerales selon la revendication 15, caracterisees en ce 1'homopolymere de 1'acide acrylique mis en oeuvre, possede une masse moleculaire moyenne comprise entre 15 000 et 80 000 Daltons.  16 - Aqueous dispersions of mineral matter according to claim 15, characterized in that the homopolymer of the acrylic acid used, has an average molecular mass of between 15,000 and 80,000 Daltons. 17 - Dispersions aqueuses de matieres minerales selon dune des revendications 1 a 16, caracterisees en ce 1'homopolymere de 1'acide acrylique, presente un taux de neutralisation, exprime en pourcentage molaire de sites acides neutralises, compris entre 10 et 100.  17 - Aqueous dispersions of mineral matter according to one of claims 1 to 16, characterized in that the homopolymer of acrylic acid, has a degree of neutralization, expressed in molar percentage of neutralized acid sites, between 10 and 100. 18 - Dispersions aqueuses de matieres minerales selon la revendication 17, caracterisees en ce 1'homopolymere de 1'acide acrylique, presente un taux de neutralisation, exprime en pourcentage molaire de sites acides neutralises, compris entre 50 et 100.  18 - Aqueous dispersions of mineral matter according to claim 17, characterized in that the homopolymer of acrylic acid, has a degree of neutralization, expressed in molar percentage of neutralized acid sites, between 50 and 100. 19 - Dispersions aqueuses de matieres minerales selon la revendication 18, caracterisees en ce 1'homopolymere de 1'acide acrylique, presente un taux de neutralisation, exprime en pourcentage molaire de sites acides neutralises, compris entre 70 et 100. - Utilisation de dispersions aqueuses de matieres minerales selon rune des revendications 1 a 19, dans la fabrication de formulations aqueuses contenant des matieres minerales. 21 - Utilisation de dispersions aqueuses de matieres minerales selon rune des revendications 1 a 19, dans le domaine du papier, et plus particulierement dans la fabrication de la feuille de papier et dans la fabrication de sauces de couchage destines a la production d'une feuille de papier couchee. 22 - Utilisation de dispersions aqueuses de matieres minerales selon rune des revendications 1 A. 19 dans le plastique. 23 -Utilisation de dispersions aqueuses de matieres minerales selon rune des revendications 1 a 19 dans la peinture. 203526 24 - Utilisation de dispersions aqueuses de matieres minerales selon rune des revendications 1 a 19 Bans la fabrication de pates dentaires.  19 - Aqueous dispersions of mineral matter according to claim 18, characterized in that the homopolymer of acrylic acid, has a degree of neutralization, expressed in molar percentage of neutralized acid sites, between 70 and 100. - Use of aqueous dispersions mineral material according to one of claims 1 to 19 in the manufacture of aqueous formulations containing mineral matter. 21 - Use of aqueous dispersions of mineral matter according to one of claims 1 to 19, in the field of paper, and more particularly in the manufacture of the paper sheet and in the manufacture of coating coatings intended for the production of a sheet layered paper. 22 - Use of aqueous dispersions of minerals according to rune of claims 1 A. 19 in the plastic. 23 -User aqueous dispersions of mineral materials according to rune of claims 1 to 19 in the paint. 203526 24 - Use of aqueous dispersions of minerals according to rune of claims 1 to 19 B in the manufacture of toothpastes.
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FR2939055A1 (en) * 2008-12-03 2010-06-04 Coatex Sas Use of a mineral material, homopolymer or copolymer of acrylic acid, as dispersing agent and/or grinding aid agent, where the acrylic acid is obtained from glycerol

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EP0850685A2 (en) * 1996-12-27 1998-07-01 Ecc International Limited Dispersed aqueous suspensions
WO2000039029A2 (en) * 1998-12-23 2000-07-06 Imerys Minerals Ltd. Production of concentrated carbonate suspensions
WO2001048093A1 (en) * 1999-12-27 2001-07-05 Coatex S.A.S. Use of water soluble polymers as dispersion agent of aqueous calcium carbonate suspension, resulting aqueous suspensions and their uses

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US4219590A (en) * 1977-01-20 1980-08-26 Shiraishi Kogyo Kaisha, Ltd. Method for improving calcium carbonate
EP0850685A2 (en) * 1996-12-27 1998-07-01 Ecc International Limited Dispersed aqueous suspensions
WO2000039029A2 (en) * 1998-12-23 2000-07-06 Imerys Minerals Ltd. Production of concentrated carbonate suspensions
WO2001048093A1 (en) * 1999-12-27 2001-07-05 Coatex S.A.S. Use of water soluble polymers as dispersion agent of aqueous calcium carbonate suspension, resulting aqueous suspensions and their uses

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2939055A1 (en) * 2008-12-03 2010-06-04 Coatex Sas Use of a mineral material, homopolymer or copolymer of acrylic acid, as dispersing agent and/or grinding aid agent, where the acrylic acid is obtained from glycerol

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