Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/0004—Preparation of sols
  • B01J13/0034—Additives, e.g. in view of promoting stabilisation or peptisation
• • 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
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D17/00—Pigment pastes, e.g. for mixing in paints
  • C09D17/001—Pigment pastes, e.g. for mixing in paints in aqueous medium
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D17/00—Pigment pastes, e.g. for mixing in paints
  • C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/45—Anti-settling agents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
  • C09K23/017—Mixtures of compounds
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/30—Particle morphology extending in three dimensions
  • C01P2004/39—Particle morphology extending in three dimensions parallelepiped-like
• • 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
  • C01P2004/61—Micrometer sized, i.e. from 1-100 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
  • C01P2006/12—Surface area
• • 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

Definitions

• a first object of the invention resides in the use as a dispersing agent, for the purpose of dispersing precipitated calcium carbonate (PCC) -based mineral substances in water, of a combination:
• a second and a third subject of the invention reside in the aqueous suspensions of PCC-containing mineral matter thus obtained, and in the dry pigments obtained by drying said suspensions.
• a final object of the invention resides in the use of the aforementioned dry suspensions and pigments in the manufacture of paper, and in particular in the formulation of paper coating coatings and in the manufacture of the paper sheet, in the manufacture of paints , plastics and rubbers.
• PCC calcium carbonate, more precisely precipitated calcium carbonate (PCC) is a filler commonly used in many applications such as plastic, paint, but also paper, giving the latter good optical properties and printability.
• PCC is a synthetic material, generally obtained by precipitation in water by reaction between carbon dioxide and lime, the result being an aqueous suspension of PCC.
• the dry extract of said aqueous suspension is defined as the percentage by dry weight of PCC relative to the total weight of said suspension (this definition will be repeated throughout the present Application). In order to provide the user with the greatest possible amount of PCC per unit volume, the skilled person seeks to maximize this dry extract.
• this aqueous suspension containing PCC during its transport, will undergo a number of transfer steps from one tank to another, in particular via pumping operations. It is therefore necessary for said dispersion to be pumpable, which results in a particular rheological behavior: this stress can be likened to obtaining an instant Brookfield TM viscosity, measured at 25 ° C. and at 100 rpm according to the method well known in the art, the lowest possible.
• the Applicant indicates that throughout the rest of the application, the Brookfield TM viscosity term will denote the Brookfield TM viscosity measured immediately at 25 ° C and 100 revolutions / minute, with the appropriate module and according to the method well known to man of career.
• the Applicant has not indicated a particular value for the dry extract and the Brookfield TM viscosity that the skilled person seeks to maximize and reduce respectively. Indeed, it is not possible to give general values because they depend (among others) on the crystal structure of the envisaged PCC (the PCC may be a rhombohedron, a scalenohedron, aragonite or vaterite ), its particle size characteristics and its specific surface area.
• the Applicant does not wish to mislead the reader by indicating particular values that might suggest that the search for said values is precisely the technical problem that the present Application seeks to solve: the real technical problem referred to in the present application. This application will be indicated and detailed in the following paragraph.
• a dispersing agent is all the more effective if it is necessary to use a smaller quantity to obtain a given Brookfield TM solids content and viscosity, this quantity being expressed as a percentage by dry weight of dispersing agent per ratio to the total dry weight of PCC.
• the problem that the present Application seeks to solve can be defined as the search for dispersing agents of PCC, which are more effective than those of the prior art: that is to say dispersing agents whose Those skilled in the art will be able to use a smaller quantity than that relating to the dispersing agents of the prior art, with a view to achieving a given Brookfield TM solids content and viscosity, for the aqueous dispersion of PCC that it seeks to obtain.
• the document EP 0 401 790 describes aqueous suspensions of mineral materials, produced by adding a polymer, in particular of cationic nature.
• the mineral materials in question include calcium carbonate, either in natural form or in precipitated form (although there is no example for PCC).
• the document WO 99/61374 describes an aqueous suspension of precipitated calcium carbonate, the pH of which is stabilized at a value of less than 9 and presenting a positive zeta potential: a suspension is obtained which has a good adhesion capacity of the particles of PCC on cellulose fibers.
• the proposed solution consists in the use of a monocarboxylic acid of formula A-COOH, where A denotes hydrogen, or an alkyl radical having from 1 to 8 carbon atoms.
• the examples indicate dry extracts equal to 30% of the total weight of the aqueous suspensions of PCC, and remain silent on the viscosities of such suspensions.
• DE 10 253 812 discloses an aqueous suspension of PCC and calcium sulfate which are used in offset printing, said suspension containing also a dispersing agent and a grinding aid agent, which are selected from polyacrylates, polyvinyl alcohol, polycarboxylic acids, polysaccharides, and derivatives thereof. It is stated that such a process makes it possible to obtain easily pumpable suspensions while no viscosity measurement is indicated, having a high solids content without any value being mentioned, and finally making it possible to reduce by 60% the energy efficiency of the dispersion process: the document does not contain any example that would demonstrate these properties, and is therefore of no help to the skilled person.
• the document EP 1 160 294 describes a method making it possible to obtain an aqueous suspension of mineral particles, having an improved rheology with a low gradient of speed, which makes it possible to increase its dry extract, and with a high speed gradient which makes the products usable on paper coating machines working at high speed (the machinability is thus improved).
• This method is based on the implementation of a grinding step using a rotor-stator type mill.
• the suspension of mineral fillers is previously dispersed by means of phosphate compounds, polyacrylates, sulphonates, silicates and ligno-sulphates, the preferred dispersing agent being a sodium polyacrylate.
• the document WO 96/32448 describes a method for manufacturing PCC suspensions subsequently implemented in paper coating coatings by the use of an anionic dispersing agent based on polycarboxylic acid, such as a homo or copolymer.
• an anionic dispersing agent based on polycarboxylic acid such as a homo or copolymer.
• (meth) acrylic acid leading to a suspension whose solids content is less than 30% of its weight the addition of a cationic agent based on quaternary amines to aggregate the PCC particles, and finally the partial elimination of water leading to a final suspension whose solids content is greater than 60% of its weight.
• a cationic agent based on quaternary amines to aggregate the PCC particles
• the partial elimination of water leading to a final suspension whose solids content is greater than 60% of its weight examples which relate exclusively to a natural calcium carbonate do not inform the skilled person on the implementation of this invention in the context of the PCC.
• the document KR 2003 60301 describes a method for preparing suspensions of PCC, by reaction in water of Ca (OH) 2 and carbon dioxide, by the formation of a filter cake whose solids content is between 35 and 40% of its weight, by adding a dispersant which is a polyacrylate, and by obtaining an aqueous suspension whose solids content is between 60 and 65% of its weight, stable over time and having a low viscosity.
• the document WO 02/13774 describes an aqueous suspension of PCC that can be used in the formulation of dental pastes.
• This suspension contains in particular an antimicrobial agent, and a dispersing agent in the preferred form of a combination of 0.1 to 0.7% by weight (based on the dry weight of PCC) of sodium hexametaphosphate and 0 , 8 to 1.2% by weight (based on the dry weight of PCC) of sodium hypochlorite.
• the only example shows that one can obtain, by mixing 236 g of a suspension of PCC whose dry extract is equal to 20% of its weight, and 3 kg of a cake of PCC whose extract dry is equal to 70% of its weight, a final suspension whose solids content is therefore equal to 66.4% (there is no mention of the particle size of the PCC used), said suspension containing 0.4 % by weight of sodium hexametaphosphate and 0.015% by weight of sodium hypochlorite.
• the suspension thus obtained has a Brookfield TM viscosity equal to 250 mPa.s.
• the document WO 00/39029 describes a method for obtaining an aqueous suspension of a carbonate material and in particular PCC, having a high solids content, which is sufficiently fluid to be easily pumpable and sufficiently viscous to avoid undesirable sedimentation phenomena.
• This process consists of a step a) of suspending the precipitated calcium carbonate at a solids content of not more than 40%, a step b) of partial removal of the water to reach a solids content of between 45 and 65% , a step c) of addition of a dispersing agent, a new step d) partial elimination of water, and finally a step e) mechanical treatment by high speed mixing dissipating at least 1 kW / hour by a ton of PCC.
• aqueous suspension of PCC 75% by weight of the particles of which have a diameter of less than 0.5 ⁇ m, with a solids content equal to 71% of the total weight of the suspension, the viscosity remains stable for at least 7 days, said suspension being easily handled and in particular pumpable.
• this example implements 0.5% by weight of a sodium polyacrylate (relative to the dry weight of PCC)
• polymers containing at least one group of the carboxylic acid type such as (meth) acrylic, itaconic, crotonic, fumaric acid, maleic, isocrotonic, angelic, undecylenic, hydroxy-acrylic, or maleic anhydride
• said polymers having a molecular weight preferably less than 20,000 g / mol.
• the Applicant intends either a fluorinated mineral compound or hydrofluoric acid, or a compound which is an ammonium fluoride or phosphonium.
• this combination of at least one homopolymer and / or at least one copolymer of (meth) acrylic acid and / or at least one phosphate compound and / or at least one cationic polymer with a fluoride ion-bearing compound proves to be more effective as a dispersant of PCC-containing inorganic materials in water than the simple use of a homopolymer and / or a copolymer of (meth) acrylic acid and / or a phosphate compound and / or a cationic polymer.
• the amount of dispersing agent according to the invention (sum of the percentage by dry weight of the homopolymer and / or of the copolymer of (meth) acrylic acid and / or of the phosphate compound and / or of the cationic polymer and the dry weight percentage of the fluoride ion carrier compound) is lower than the amount of dispersing agent according to the prior art (dry weight percentage of the homopolymer and / or the copolymer of the (meth) acrylic acid and and / or the phosphate compound and / or the cationic polymer), in order to obtain an aqueous dispersion of PCC-containing mineral matter having a given solids content and a given Brookfield TM viscosity, these percentages being given relative to the total dry weight of PCC used.
• the Applicant believes that the fluoride ion carrier compound used in the composition of the dispersing agent according to the invention has, when it is brought into contact with the PCC, a high reactivity to screw of the latter. This hypothesis is supported by the extremely low value of the solubility product of fluorite (3.45 10-11 , according to the Handbook of Chemistry and Physics, 78 th Ed., 1997-1998) which must result from this reaction between the PCC.
• One of the merits of the Applicant is in particular that it has been able to identify a particular compound, in the form of a fluoride ion-bearing compound and which, in combination with a homo- and / or a copolymer of the acid (meth) acrylic and / or a phosphate compound and / or a cationic polymer, reduces the amount of total dispersant used (as previously expressed) to obtain a given Brookfield TM solids content and viscosity.
• a first object of the invention lies in the use as dispersing agent, for the purpose of dispersing in water mineral matter containing precipitated calcium carbonate (PCC), characterized in that said dispersing agent is the combination:
• This use is also characterized in that said combination is implemented, with a view to dispersing in water precipitated calcium carbonate (PCC) -based minerals: a) during a dispersion step in the water of PCC initially introduced as a dry powder, b) and / or during a step of dispersion in water of a PCC filter cake, c) and / or during a concentration / dispersion stage of a suspension aqueous PCC.
• PCC water precipitated calcium carbonate
• the use of dispersing agent according to the invention is also characterized in that the fluoride ion-bearing compound is chosen from ammonium and / or phosphonium fluorides and / or from the compounds NaF, HF, KF and NaHF. 2 , H 2 SiF 6 , HKF 2 , FeF 2 , PbF 2 , HNH 4 F 2 and mixtures thereof, preferentially from the compounds NaF, HF, KF, H 2 SiF 6 , HKF 2 , and mixtures thereof, and that it is preferably selected from the compounds NaF and HF and mixtures thereof.
• the fluoride ion-bearing compound is chosen from ammonium and / or phosphonium fluorides and / or from the compounds NaF, HF, KF and NaHF. 2 , H 2 SiF 6 , HKF 2 , FeF 2 , PbF 2 , HNH 4 F 2 and mixtures thereof, preferentially from the compounds NaF, HF,
• dispersing agent according to the invention is also characterized in that the copolymer of (meth) acrylic acid comprises at least one other monomer chosen from at least: a) another anionic monomer, b) and / or at least one cationic monomer, c) and / or at least one nonionic monomer.
• the other anionic monomer a) is chosen from an anionic monomer with ethylenic unsaturation and monocarboxylic functional group in the acid or salified state, chosen from monomers with ethylenic unsaturation and monocarboxylic function, and preferably from the acid acrylic, methacrylic, crotonic, isocrotonic, cinnamic or the half-esters of diacids such as C 1 -C 4 monoesters maleic or itaconic acid, or selected from monomers with ethylenic unsaturation and dicarboxylic function in the acidic or salified state, and preferentially among itaconic acid, maleic acid, fumaric acid, mesaconic acid, or also anhydrides of carboxylic acids, such as maleic anhydride or chosen from ethylenically unsaturated monomers and with a sulphonic function in the acidic or salified state, and preferentially from acrylamido-2-methyl-2-prop
• the cationic monomer b) is chosen from quaternary ammoniums, and preferably from [2- (methacryloyloxy) ethyl] trimethyl ammonium chloride or sulphate, [2- (acryloyloxy) ethyl] chloride or sulphate. trimethylammonium, [3- (acrylamido) propyl] trimethylammonium chloride or sulphate, dimethyl diallyl ammonium chloride or sulphate, [3- (methacrylamido) propyl] trimethyl ammonium chloride or sulphate or mixtures thereof .
• the nonionic monomer c) is chosen from N- [3- (dimethylamino) propyl] acrylamide or N- [3- (dimethylamino) propyl] methacrylamide, unsaturated esters such as N- methacrylate [ 2- (dimethylamino) ethyl], or N- [2- (dimethylamino) ethyl] acrylate, or among acrylamide or methacrylamide and mixtures thereof, alkyl acrylates or methacrylates, vinyl monomers, and preferentially vinyl, vinylpyrrolidone, styrene, dimethyl-styrene and their derivatives, or the monomers of formula (I):
• n and p represent a number of alkylene oxide units of less than or equal to 150, n represents a number of ethylene oxide units less than or equal to
• q represents an integer at least equal to 1 and such that 5 ⁇ (m + n + ⁇ ) q ⁇
• R 1 represents hydrogen or the methyl or ethyl radical
• R 2 represents hydrogen or the methyl or ethyl radical
• R represents a radical containing a polymerizable unsaturated functional group, preferably belonging to the vinyl group as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters, as well as to the group of unsaturated urethanes such as acrylurethanes, methacrylurethane, ⁇ ⁇ -dimethylisopropenylbenzylurethane, allyl urethane, as well as the group of substituted or unsubstituted allylic or vinyl ethers, or else the group of ethylenically unsaturated amides or imides,
• R ' represents hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms.
• the use of dispersing agent according to the invention is also characterized in that the homopolymer and / or the copolymer of (meth) acrylic acid is neutralized, totally or partially, with a neutralization agent chosen from sodium hydroxides. , potassium, hydroxides and / or oxides of calcium, magnesium, ammonia, or mixtures thereof, preferably with a neutralizing agent chosen from hydroxides of sodium or potassium, ammonia, or mixtures thereof, very preferably by a neutralizing agent which is sodium hydroxide.
• dispersing agent is also characterized in that the cationic polymer consists of at least one monomer chosen from quaternary ammoniums, and preferably from [2- (methacryloyloxy) ethyl chloride or sulphate. ] trimethylammonium chloride, [2- (acryloyloxy) ethyl] trimethylammonium chloride or sulphate, [3- (acrylamido) propyl] trimethylammonium chloride or sulphate, dimethyl diallyl ammonium chloride or sulphate, chloride or [3- (methacrylamido) propyl] trimethyl ammonium sulfate, or mixtures thereof.
• dispersing agent according to the invention is also characterized in that the phosphate compound is chosen from polyphosphates and preferably from tripolyphosphates, or hexametaphosphates or pyrophosphates, sodium or potassium, or mixtures thereof.
• dispersing agent according to the invention is also characterized in that between 0.1% and 5.0%, by dry weight relative to the dry weight of mineral matter, of at least one homopolymer and / or at least one copolymer of (meth) acrylic acid and / or at least one phosphate compound and / or at least one cationic polymer.
• dispersing agent according to the invention uses between 0.01% and 0.5%, and preferably between 0.05% and 0.25%, by dry weight per relative to the dry weight of mineral matter, at least one fluoride ion-bearing compound.
• the use of dispersing agent according to the invention is also characterized in that the fluoride ion carrier compound on the one hand and the rhomopolymer and / or the copolymer of (meth) acrylic acid and / or the phosphate compound and / or the cationic polymer, on the other hand, are introduced simultaneously or sequentially (sequenced meaning that they are introduced one after the other).
• the use of dispersing agent according to the invention is also characterized in that the fluoride ion-bearing compound on the one hand, and the homopolymer and / or the copolymer of (meth) acrylic acid, and / or the phosphate compound, and / or the cationic polymer, on the other hand, are introduced simultaneously, both in the form of an aqueous suspension and / or an aqueous solution and / or in the form of of dry powder, or are introduced simultaneously and in a mixture, said mixture being an aqueous suspension and / or an aqueous solution and / or a dry powder.
• the use of dispersing agent according to the invention is also characterized in that the fluoride ion-bearing compound is introduced in the form of a dry powder and / or in the form of an aqueous suspension. and / or in the form of an aqueous solution, and in that the homopolymer and / or the copolymer of the (meth) acrylic acid, and / or the phosphate compound, and / or the cationic polymer, on the other hand, is introduced in the form of an aqueous solution and / or in the form of a dry powder when these two compounds are introduced sequentially that is to say one after the other and this, whatever the order of introduction .
• dispersing agent according to the invention is also characterized in that the homopolymer and / or the copolymer of (meth) acrylic acid is obtained by known methods of solution radical polymerization, in direct or inverse emulsion, in suspension or precipitation in appropriate solvents, in the presence of known catalytic systems and transfer agents, or by controlled radical polymerization processes such as the so-called Reversible Addition Fragmentation Transfer (RAFT) method, the method called Atom Transfer Radical Polymerization (ATRP), the method called Nitroxide Mediated Polymerization (NMP), the method called Macromolecular Design via Interchange of Xanthates (MADIX) or the method called Cobaloxime Mediated Free Radical Polymerization.
• RAFT Reversible Addition Fragmentation Transfer
• ATRP Atom Transfer Radical Polymerization
• NMP Nitroxide Mediated Polymerization
• MADIX Macromolecular Design via Interchange of Xanthates
• Cobaloxime Mediated Free Radical Polymerization
• dispersing agent according to the invention is also characterized in that the homopolymer and / or the copolymer of the (meth) acrylic acid may, optionally before or after its total or partial neutralization, be treated and separated into several phases, according to static or dynamic processes known to those skilled in the art, by one or more polar solvents preferentially belonging to the group consisting of water, methanol, ethanol, propanol, isopropanol, butanols, acetone , tetrahydrofuran or their mixtures.
• One of the two phases then corresponds to the polymer used according to the invention.
• dispersing agent according to the invention is also characterized in that the aqueous suspension of mineral matter containing PCC contains at least one PCC of the rhombohedron, scalenohedron, vateric or aragonitic type or their mixtures.
• a dispersing agent according to the invention is also characterized in that the aqueous suspension of mineral matter containing PCC contains at least 2 PCCs of different particle size characteristics, as measured from a commercially available Sedigraph TM 5100 device. by MICROMERITICS TM.
• dispersing agent is also characterized in that the aqueous suspension of mineral matter containing PCC, optionally contains at least one other mineral material chosen from natural calcium carbonate, dolomites, kaolin, talc, gypsum, lime, magnesia, titanium dioxide, white satin, aluminum trioxide or aluminum trihydroxide, silicas, mica and the mixture of these fillers together, as mixtures talc-calcium carbonate, calcium carbonate-kaolin, or mixtures of calcium carbonate with aluminum trihydroxide or aluminum trioxide, or mixtures with synthetic or natural fibers or co-structures of minerals such as talc-calcium carbonate or talc-titanium co-strucrures, or mixtures thereof, and preferably in that it is a natural calcium carbonate which is preferably chosen from marble, calcite, chalk or their mixtures.
• the molecular weight, the polymolecularity index, the neutralization agent and the degree of neutralization of the phosphate compound and / or
• MICROMERITICS TM its particle size characteristics such as in particular its median diameter (measured according to a Sedigraph TM 5100 device marketed by MICROMERITICS TM).
• Another subject of the invention resides in the aqueous suspensions of mineral matter containing PCC, and also containing as dispersing agent the combination of: at least one homopolymer and / or at least one copolymer of the acid (meth) ) acrylic, and / or at least one phosphate compound, and / or at least one cationic polymer, and at least one fluoride ion-bearing compound.
• the aqueous suspensions of mineral matter according to the invention are also characterized in that the fluoride ion-bearing compound is chosen from ammonium and / or phosphonium fluorides and / or from the compounds NaF, HF, KF and NaHF 2. , H 2 SiF 6 , HKF 2 , FeF 2 , PbF 2 , HNH 4 F 2 and mixtures thereof, preferentially from the compounds NaF, HF, KF, H 2 SiF 6 , HKF 2 , and mixtures thereof, and in that it is preferably selected from the compounds NaF and HF and mixtures thereof.
• the fluoride ion-bearing compound is chosen from ammonium and / or phosphonium fluorides and / or from the compounds NaF, HF, KF and NaHF 2. , H 2 SiF 6 , HKF 2 , FeF 2 , PbF 2 , HNH 4 F 2 and mixtures thereof, preferentially from the compounds NaF,
• the aqueous suspensions of mineral matter according to the invention are also characterized in that the copolymer of (meth) acrylic acid comprises at least one other monomer chosen from at least: a) another anionic monomer, b) and / or at least one cationic monomer, c) and / or at least one nonionic monomer.
• the other anionic monomer a) is chosen from an anionic monomer with ethylenic unsaturation and monocarboxylic functional group in the acid or salified state, chosen from monomers with ethylenic unsaturation and monocarboxylic function, and preferably from the acid acrylic, methacrylic, crotonic, isocrotonic, cinnamic or the half-esters of diacids such as C 1 -C 4 monoesters maleic or itaconic acid, or selected from monomers with ethylenic unsaturation and dicarboxylic function in the acidic or salified state, and preferentially among itaconic acid, maleic acid, fumaric acid, mesaconic acid, or also anhydrides of carboxylic acids, such as maleic anhydride or chosen from ethylenically unsaturated monomers and with a sulphonic function in the acidic or salified state, and preferentially from acrylamido-2-methyl-2-prop
• the cationic monomer b) is chosen from quaternary ammoniums, and preferably from [2- (methacryloyloxy) ethyl] trimethyl ammonium chloride or sulphate, [2- (acryloyloxy) ethyl] chloride or sulphate. trimethylammonium, [3- (acrylamido) propyl] trimethylammonium chloride or sulphate, dimethyl diallyl ammonium chloride or sulphate, [3- (methacrylamido) propyl] trimethyl ammonium chloride or sulphate or mixtures thereof .
• the nonionic monomer c) is chosen from N- [3- (dimethylamino) propyl] acrylamide or N- [3- (dimethylamino) propyl] methacrylamide, unsaturated esters such as N- methacrylate [ 2- (dimethylamino) ethyl], or N- [2- (dimethylamino) ethyl] acrylate, or from acrylamide or methacrylamide and mixtures thereof, alkyl acrylates or methacrylates, vinyl monomers, and preferentially vinyl acetate, vinylpyrrolidone, styrene, p-methylstyrene and their derivatives, or the monomers of formula (I):
• m and p represent a number of alkylene oxide units of less than or equal to 150
• n represents a number of ethylene oxide units of less than or equal to 150
• q represents an integer at least equal to 1 and such that 5 ⁇ (m + n + ⁇ ) q ⁇ 150, and preferentially such that ⁇ (m + n + p) q ⁇ 120
• R 1 represents hydrogen or the methyl or ethyl radical
• R 2 represents hydrogen or the methyl or ethyl radical
• R represents a radical containing a polymerizable unsaturated functional group, preferably belonging to the vinyl group as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic and vinylphthalic esters, as well as to the group of unsaturated urethanes such as acrylurethanes, methacrylurethane, ⁇ - ⁇ -dimethylisopropenylbenzylurethane, allylurethane, as well as
• R ' represents hydrogen or a hydrocarbon radical having 1 to 40 carbon atoms.
• the aqueous suspensions of mineral matter according to the invention are also characterized in that the homopolymer and / or the copolymer of (meth) acrylic acid is neutralized, totally or partially, by a neutralization agent chosen from hydroxides of sodium, potassium, hydroxides and / or oxides of calcium, magnesium, ammonia, or mixtures thereof, preferably with a neutralizing agent selected from hydroxides of sodium or potassium, ammonia, or mixtures thereof, very preferably with a neutralizing agent which is sodium hydroxide.
• a neutralization agent chosen from hydroxides of sodium, potassium, hydroxides and / or oxides of calcium, magnesium, ammonia, or mixtures thereof, preferably with a neutralizing agent selected from hydroxides of sodium or potassium, ammonia, or mixtures thereof, very preferably with a neutralizing agent which is sodium hydroxide.
• the aqueous suspensions of mineral matter according to the invention are also characterized in that the cationic polymer consists of at least one monomer chosen from quaternary ammonium, and preferably from [2- (methacryloyloxy) ethyl chloride or sulphate] trimethylammonium chloride, [2- (acryloyloxy) ethyl] trimethyl ammonium chloride or sulphate, [3- (acrylamido) propyl] trimethyl ammonium chloride or sulphate, dimethyl diallyl ammonium chloride or sulphate, chloride or [3- (methacrylamido) propyl] trimethyl ammonium sulfate, or mixtures thereof.
• the cationic polymer consists of at least one monomer chosen from quaternary ammonium, and preferably from [2- (methacryloyloxy) ethyl chloride or sulphate] trimethylammonium chloride, [2- (acryloyloxy
• aqueous suspensions of mineral matter according to the invention are also characterized in that the phosphate compound is chosen from polyphosphates and preferably from tripolyphosphates, or hexametaphosphates or pyrophosphates, sodium or potassium, or mixtures thereof.
• aqueous suspensions of mineral matter according to the invention are also characterized in that they contain between 0.1% and 5.0%, by dry weight relative to the dry weight of mineral matter, of at least one homopolymer and / or or at least one copolymer of (meth) acrylic acid and / or at least one phosphate compound and / or at least one cationic polymer.
• aqueous suspensions of mineral matter according to the invention 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 weight. dry mineral materials, at least one fluoride ion carrier compound.
• the aqueous suspensions of mineral matter according to the invention are also characterized in that the homopolymer and / or the copolymer of (meth) acrylic acid is obtained by known methods of solution radical polymerization, in direct or inverse emulsion, in suspension or precipitation in appropriate solvents, in the presence of known catalytic systems and transfer agents, or by controlled radical polymerization processes such as the so-called Reversible Addition Fragmentation Transfer (RAFT) method, the method called Atom Transfer Radical Polymerization (ATRP), the method called Nitroxide Mediated Polymerization (NMP), the method called Macromolecular Design via Interchange of Xanthates (MADIX) or the method called Cobaloxime Mediated Free Radical Polymerization.
• RAFT Reversible Addition Fragmentation Transfer
• ATRP Atom Transfer Radical Polymerization
• NMP Nitroxide Mediated Polymerization
• MADIX Macromolecular Design via Interchange of Xanthates
• the aqueous suspensions of mineral matter according to the invention are also characterized in that the homopolymer and / or the copolymer of the (meth) acrylic acid may, optionally before or after its total or partial neutralization, be treated and separated into several phases. according to static or dynamic processes known to those skilled in the art, by one or more polar solvents preferentially belonging to the group consisting of water, methanol, ethanol, propanol, isopropanol, butanols, acetone, tetrahydrofuran or mixtures thereof. One of the phases then corresponds to the polymer used according to the invention.
• aqueous suspensions of mineral matter according to the invention are also characterized in that they contain at least one PCC of the rhombohedron, scalenohedron, vateric, aragonitic or mixtures thereof type.
• aqueous suspensions of mineral matter according to the invention are also characterized in that they contain at least 2 PCC of different particle size characteristics, as measured from a Sedigraph TM 5100 device marketed by MICROMERITICS TM.
• the aqueous suspensions of mineral matter according to the invention are also characterized in that they optionally contain at least one other mineral material that the PCC chosen from natural calcium carbonate, dolomites, kaolin, talc, gypsum, lime, magnesia, titanium dioxide, white satin, aluminum trioxide, silicates, mica and the mixture of these fillers with one another, such as talc-calcium carbonate, calcium carbonate-kaolin mixtures, or mixtures of calcium carbonate with aluminum trihydroxide or aluminum trioxide, or mixtures with synthetic or natural fibers or co-structures of minerals such as talc-calcium carbonate or talc-titanium dioxide co-structures, or mixtures thereof and preferably in that it is a natural calcium carbonate which is preferably selected from marble, calcite, chalk or mixtures thereof.
• the PCC chosen from natural calcium carbonate, dolomites, kaolin, talc, gypsum, lime, magnesia, titanium dioxide, white satin, aluminum trioxid
• aqueous suspensions of mineral matter according to the invention mentioned above can also undergo an additional processing step, among those well known to those skilled in the art.
• Another subject of the invention is a process for manufacturing pigments containing PCC, characterized in that an aqueous suspension of inorganic materials containing PCC according to the invention undergoes at least one additional treatment step, chosen from:
• a mixing step with another dispersion and / or aqueous suspension containing a mineral material, which is preferably natural calcium carbonate or kaolin or mixtures thereof, a grinding step, a step of co-grinding with another mineral material which is preferably natural calcium carbonate, - a step of mechanical and / or thermal concentration, a drying step.
• a mineral material which is preferably natural calcium carbonate or kaolin or mixtures thereof
• the dry pigments resulting from a step of drying said aqueous suspensions of mineral materials is also another object of the present invention.
• Another object of the invention resides in the uses of the aqueous suspensions of minerals containing PCC mentioned above and in those of dry pigments. above, in a process for producing aqueous formulations of mineral materials or dry products containing inorganic materials.
• Another object of the invention resides in the uses of the aqueous suspensions of the above-mentioned PCC-containing inorganic materials and in those of the aforementioned dry pigments, in a process for manufacturing paper coating coatings.
• Another object of the invention resides in the uses of the aqueous suspensions of the aforementioned PCC-containing inorganic materials and in those of the aforementioned dry pigments, in a method of manufacturing the paper sheet.
• Another object of the invention resides in the uses of the aqueous suspensions of the aforementioned PCC-containing inorganic materials and in those of the aforementioned dry pigments, in a method of manufacturing paints.
• Another object of the invention lies in the uses of the aqueous suspensions of mineral matter containing PCC mentioned above and in those of the aforementioned dry pigments, in a process for the manufacture of plastics or rubbers (it goes without saying that these are the dry pigments, and not aqueous suspensions, which are used in the manufacture of said dry products).
• the polymolecularity index and the molecular weight of the polymers used are determined according to the method explained below.
• the molecular weight and the polymolecularity index are determined by a method of size exclusion chromatography (CES), as follows. 1 ml of the polymer solution is put on a cup, which is then evaporated at room temperature under a vane pump vacuum. The solute is taken up in 1 ml of the eluent of the CES, and the whole is then injected into the CES apparatus.
• the eluent of the CES is a solution of NaHCO 3 : 0.05 mol / L, NaNO 3 : 0.1 mol / L, triethylamine 0.02 mol / L, NaN 3 0.03% by weight.
• the CES chain contains an isocratic pump (Waters TM 515) whose flow rate is set at 0.5 mL / min, an oven containing a precolumn of "Guard Column Ultrahydrogel Waters TM” type, a linear column of 7.8 mm internal diameter and 30cm of length type “Ultrahydrogel Waters TM” and a refractometric detector type RI Waters TM 410. The oven is heated to 60 0 C and the refractometer to 50 ° C.
• the chromatogram detection and processing software is the SECential software, provided by "LMOPS CNRS, Chemin du Canal, Vernaison, 69277".
• the CES is calibrated by a series of 5 standards of sodium poly (acrylate) supplied by Polymer Standards Service TM.
• This example illustrates the manufacture of an aqueous dispersion of precipitated calcium carbonate, by forming an aqueous suspension of PCC with a solids content equal to 17% of its total weight, and then forming a filter cake with a dry extract equal to 50% of its total weight, and finally dispersion of said filter cake:
• This example illustrates the manufacture of an aqueous dispersion of precipitated calcium carbonate, by aqueous formation of an aqueous suspension of PCC with a solids content equal to 20% of its total weight, and then formation of a filter cake with an extract dry equal to 38% of its total weight, and finally dispersion of said filter cake:
• This example illustrates the manufacture of an aqueous dispersion of precipitated calcium carbonate, by aqueous formation of an aqueous suspension of PCC with a solids content equal to 34% of its total weight: according to the prior art, by addition of hexametaphosphate of sodium, according to the invention, by adding sodium hexametaphosphate, in combination with a fluoride ion carrier compound.
• This example illustrates the manufacture of an aqueous dispersion of precipitated calcium carbonate, by forming an aqueous suspension of PCC with a solids content equal to 17% of its total weight, and then forming a filter cake with a dry extract equal to 50% of its total weight, and finally dispersion of said filter cake: according to the prior art, by adding, after the step of forming the filter cake of a phomopolymer salt of acrylic acid,
• This example is intended in particular to illustrate the particular case where the fluorinated mineral compound and the homopolymer of acrylic acid are introduced simultaneously. It is indicated that, in all the other examples supporting the present Application, the fluorinated mineral compound is introduced before the homopolymer or the copolymer of acrylic acid, or the cationic polymer or the phosphate compound.
• This example illustrates the manufacture of an aqueous dispersion of PCC carbonate, by forming an aqueous suspension of PCC with a solids content equal to 17% of its total weight, and then forming a filter cake with an equal solids content at 50% of its total weight, and finally dispersion of said filter cake:
• a cationic polymer which is a copolymer of 2-methacryloyloxyethyltrimethylammonium chloride and methacrylamidopropyltrimethylammonium chloride (95/5% by mole%) completely neutralized with ammonia, with a molecular weight equal to 91,400 g / mol and a polydispersity index equal to 4.7, in the case of test No. 17 which illustrates the prior art
• This example illustrates the manufacture of an aqueous dispersion of precipitated calcium carbonate (PCC) and natural (GCC), by co-milling between:
• an aqueous dispersion of PCC obtained according to the prior art (implementation of an acrylic polymer) or according to the invention (using sodium fluoride and the same acrylic polymer), and an aqueous dispersion of GCC containing a acrylic dispersant.
• aqueous suspension of GCC according to methods well known to those skilled in the art, using 0.27% by dry weight of a polyacrylate relative to the dry weight of GCC.
• This suspension has a dry extract equal to 74.6% (expressed in percentage by dry weight of GCC relative to the total weight of the suspension) and has particle size characteristics such that 40.3% by weight of the GCC particles have a diameter. less than 1 ⁇ m, 61.6% by weight of the GCC particles have a diameter of less than 2 ⁇ m, and such that the median diameter of the GCC particles is equal to 1.4 ⁇ m.
• An aqueous suspension of PCC is also prepared according to methods well known to those skilled in the art.
• This suspension has a dry extract equal to 14.1% (expressed as a percentage by dry weight of PCC relative to the total weight of the suspension) and has granulometric characteristics such that 83.3% by weight of PCC particles have a smaller diameter. at 1 ⁇ m, 97.8% by weight of the PCC particles have a diameter of less than 2 ⁇ m, and such that the median diameter of said PCC particles is equal to 0.58 ⁇ m. It contains :
• the aqueous suspension of GCC and PCC co-milled obtained after, introducing the same agent as that implemented during the co-grinding step; the amount of said agent used during the concentration step is equal to 0.4% by dry weight relative to the total dry weight of GCC and PCC.
• This example illustrates the manufacture of an aqueous dispersion of PCC and kaolin. It begins by forming an aqueous suspension of PCC with a solids content equal to 17% of its total weight, then forming a flrtration cake with a dry extract equal to 50% of its total weight.
• This example illustrates the manufacture of an aqueous dispersion of precipitated calcium carbonate, by forming an aqueous suspension of PCC with a solids content equal to 17% of its total weight, and then forming a filter cake with a dry extract equal to 50% of its total weight, and finally dispersion of said filter cake according to the invention, by adding after the step of forming the filter cake of an acrylic copolymer, in combination with a fluoride ion carrier compound.
• the fluoride ion-bearing compounds are in the form of an aqueous solution, with the exception of sodium fluoride which is in the form of a dry powder. .

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