MX2008007484A - Process for preparing coating slips featuring enhanced water retention and enhanced brookfieldtm viscosity, using a comb polymer having at least one grafted polyalkylene oxide function - Google Patents

Abstract

The invention concerns a process for preparing coating slips containing at least one mineral substance, at least one binder, and water, characterized in that this composition is admixed with at least one comb polymer obtained by grafting at least one polyalkylene oxide function onto the polymer chain, said chain resulting from the polymerization of at least one ethylenically unsaturated monomer. The resulting coating slips feature an increase in water retention and a reduction in Brookfield viscosity as compared with the same slips containing a prior-art water-retaining thickener.

Description

MANUFACTURING PROCESS OF RETENTION CHEMICALS WATER AND VISCOSITY BROOKFIELD IMPROVED USING A PEINE-TYPE POLYMER WITH AT LEAST ONE FUNCTION INJECTED TO POLYALYKYLENE OXIDE Field of the Invention The present invention relates to the technical field of the coating sauces involved in the manufacture of coated papers and boards from sauces, and more particularly the field of retention agents of water and the rheology modifying agents that intervene in the composition of the sauces. BACKGROUND OF THE INVENTION In the context of the manufacture of the coated sheet of paper, an aqueous composition called "coating dressing" is deposited on the surface of the support paper, containing in particular water, one or several mineral fillers, one or more agglutinants as well as various additives. After the deposit on the support, the coating has a natural tendency to transfer to the support, all or part of the water and water-soluble substances it contains. The professional, formulator of these coating sauces, then aims to reduce this migration of water and water-soluble substances to the maximum, in order to avoid an evolution of the rheology of the unused and recycled coating sauce in the process of coated Ref. 192613 We are talking about the phenomenon of "water retention" that we seek to improve, that is, in this case, to increase. Water retention agents are used for this. It is well known to use as sanitizing agents the coating sauces, starch, polyvinyl alcohol (PVOH), polymers based on carboxymethylcellulose (CMC), as well as latexes or emulsions of highly carboxylated polymers, or even polycarboxylates such as polyacrylates, or finally a particular class of expandable polymers with alkalis. This type of products, and their use as agents for improving the water retention of the paper coating sauces, are described in particular in EP 0 509 878, as an object of the invention in what refers to a mixture of expandable alkaline polymers and expandable non-alkaline polymers, and as regards the state of the art for the other polymers mentioned above. The Applicant indicates that these agents, in addition to having an action on the retention of water from the coating sauces, also behave as thickeners; for this, the professional designates them under the expression "thickeners water retention agents". However, there is a second very important requirement for the paper coating sauces formulator, which is to obtain a little high Brookfield ™ viscosity for the sauce and that, in order to obtain a product easily manipulated by the end user. Unfortunately for the professional, none of the compounds indicated above allow for constant improvement of water retention, while maintaining a Brookfield ™ viscosity of the coating dressing sufficiently low. Thus, it is particularly well known that the above-mentioned prior art products, in addition to the interesting properties conferring to the coating sauces in terms of water retention, present a limited application because of the high Brookfield ™ viscosities that are developed in these same sauces. The professional is therefore faced with the problem of optimizing the water retention and Brookfield ™ viscosity of the coating sauce, which can be summarized through the following double problem of obtaining a couple water retention / viscosity Brookfield Improved ™, i.e. obtaining: - for a given Brookfield ™ viscosity, improved (higher) water retention than with the use of a prior art water-retaining thickener in the coating dressing; - or for a given water retention, an improved (lower) Brookfield ™ viscosity than with a prior art water retaining thickener in the coating dressing.

To date, the professional knows, in order to solve this problem, only document EP 1 203 121 which describes the use for the manufacture of paper coating sauces, of water-soluble copolymers in neutral or alkaline medium and constituted by a monomer acrylic and a vinyl monomer with a glass transition temperature greater than 90 ° C, such as in particular styrene and styrenic derivatives. These copolymers allow to improve the water retention of the coating sauce and to regulate the Brookfield ™ viscosity, either in a high value or in a low value. However, this solution is limiting for the professional, since these polymers that occur in the form of acid emulsions are part of the polymers with the alkalis indicated above that must be neutralized to fulfill their function of thickener and water retainer. However, this neutralization constitutes an additional step in the use of the coating sauce: it is not only a waste of time but also of money due to the use of neutralizing agents. Therefore, to solve the problem of water retention optimization and Brookfield ™ viscosity of the coating dressing, summarized by the following dual problem of obtaining an improved Brookfield ™ water / viscosity holding pair, is say of the obtainment: for a determined Brookfield ™ viscosity, with an improved (higher) water retention than with the use of a prior art water retaining thickener in the coating dressing, or for a given water retention, with an improved Brookfield ™ viscosity (lower) than with a water-retaining thickener prior art in the coating sauce, the Applicant has developed a new coating sauces manufacturing process, containing: (a) at least a mineral matter, (b) at least one binder, (c) water, and characterized in that at least one comb-like polymer, obtained by grafting at least one polyalkylene oxide function onto the polymer chain, is introduced into the aforementioned composition. , resulting in the polymerization chain of at least one ethylenic unsaturated monomer. The process leads in a very surprising way to obtaining coating sauces with a clearly improved Brookfield ™ water retention / viscosity pair (this improvement being explained above) with respect to coated sauces containing instead of the comb-type polymer cited above a prior art water binding thickener. Finally, the Applicant wishes to indicate a certain number of documents describing the use of comb-type polymers obtained by grafting at least one polyalkylene oxide function on the polymer chain. These uses, which will be detailed below by the Applicant, occur in applications often remote from those in the paper field, and in a systematic manner to solve technical problems different from the object of this Application. Thus, the Applicant may mention EP 0 610 534 which shows the preparation of polymers obtained by copolymerization of an isocyanate monomer and of aprotic monomers, then by functionalization by amines or monoalkylated ethers of polyalkylene glycols. This type of agents are particularly effective for the grinding of organic pigments, which is a totally different field from the object of the present Application. It also indicates that document WO 00/077 058 describes polymers based on an unsaturated derivative of a mono or dicarboxylic acid, an unsaturated polyalkylene glycol derivative, an unsaturated polysiloxane compound or an unsaturated ester. These copolymers are used as dispersing agents in the suspensions aqueous mineral loads, particularly in the field of cements, field far from the field of paper. Also known is WO 2004/041 882 which describes an ionic copolymer, hydrosoluble, and having a function grafted alkoxy or hydroxy polyalkylene glycol, whose function is to disperse and / or help the grinding of pigments and / or mineral charges. The copolymer allows to obtain aqueous suspensions of the refined materials, of concentration in dry matter that can be high, of Brookfield ™ viscosity low and stable in time with the property of presenting a pigmentary surface whose ionic charge determined by titration is weak: it therefore deals with a technical problem very different from that which seeks to solve the present invention. Also known is WO 2004/041 883 which shows the use of a water-soluble and preferably weakly ionic and water-soluble copolymer, having at least one alkoxy or hydroxy polyalkylene glycol function grafted onto at least one ethylenic unsaturated monomer, as an agent that improves the gloss of the final product such as a sheet of paper or plastic material. Now, the improvement of brightness is not at all an object of the present invention. Finally, the Applicant also knows WO 2004/044022 which describes the use of a water-soluble copolymer which has of at least one alkoxy or hydroxy polyalkylene glycol function grafted onto at least one ethylenic unsaturated monomer, as an agent that improves the activation of optical bleaching in the fields of paper, textile, detergent and paint. In example 10 of this document, it is indicated that 2 polymers based on acrylic acid, methacrylic acid and methoxy polyethylene glycol methacrylate of molecular weight 2,000, improve the water retention of a paper coating sauce: this improvement is relative to a reference constituted by a coating dressing which does not contain any water retention agent of the prior art. Now, within the framework of the present Application, the case of a reference that already contains this water retention agent thickener of the prior art is considered, which constitutes a different technical problem. Nothing suggests to the practitioner in WO 2004/044 022 that comb-like polymers according to the present Application would lead to water retention values higher than those obtained with coating sauces containing a water retaining thickener of the prior art. Finally, example 10 of this document WO 2004/044 022 indicates that the Brookfield ™ viscosities of the coating sauces containing the 2 polymers described above, are "compatible with a use in the coating of paper". Nothing indicated or suggested the possibility of reducing the Brookfield ™ viscosity of the so-called sauce by adding a comb-type polymer according to the present Application, this decrease being measured with respect to the same sauce, which contains a prior art water-retaining thickener.

BRIEF DESCRIPTION OF THE FIGURES FIG. 1 and FIG. 2 show the viscosity data against the relative increase in water retention for several tests represented in Table 1. Detailed Description of the Invention Also, a first object of the invention is to both a process for manufacturing coating sauces, the sauces containing: (a) at least one mineral matter, (b) at least one binder, (c) water, characterized in that it is introduced in the composition mentioned above, as an agent that allows increase water retention and reduce the Brookfield ™ viscosity of the composition, at least one comb-type polymer, obtained by grafting at least one polyalkylene oxide function onto the polymer chain, resulting in the polymerization chain of at least one monomer ethylenic unsaturated. The process according to the invention is also characterized in that the polymer is introduced: 1. with the mineral matter, in the form of dry powder, and / or aqueous dispersion and / or aqueous suspension resulting from the steps of: - milling and / or dispersion in a moist and preferably aqueous medium of the mineral material in the presence of the polymer, and optionally in the presence of at least one wet milling agent and / or at least one dispersing agent, leading to the production of a dispersion and / or an aqueous suspension of the mineral material; - and in the case of dry powder only, of the drying of the dispersion and / or of the aqueous suspension of the mineral matter, and then optionally treatment and classification of the obtained powder; 2. and / or with the mineral matter, in the form of aqueous dispersion and / or aqueous suspension, resulting from the steps of: - dry milling the mineral filler, optionally in the presence of at least one dry milling agent , and then eventually treatment and classification of the powder obtained; - dispersion and / or aqueous suspension of the powder obtained, with introduction of the polymer and possibly in the presence of a dispersing agent; 3. and / or with the mineral material in the form of dry powder, and / or aqueous dispersion and / or aqueous suspension resulting from the steps of: introducing the polymer into a dispersion and / or an aqueous suspension containing the mineral matter; - and in the case of dry powder only, of the drying of the dispersion and / or of the aqueous suspension of the mineral matter, and then eventually treatment and classification of the powder obtained; 4. and / or in the form of dry powder mixed with the other components a), b) and e); 5. and / or in the form of an aqueous solution mixed with the other components a), b) and e). The process according to the invention is also characterized in that the coating sauce: (a) contains from 3 parts to 20 parts, preferably from 5 parts to 15 parts by dry weight of binder, per 100 parts by dry weight of mineral matter, (b) ) contains from 0.1 parts to 2 parts, preferably from 0.1 to 1.5 parts by dry weight of comb-like polymer, per 100 parts by dry weight of mineral matter, (c) contains water in an amount by weight included between 20% and 80%. %, with respect to the total weight of the coating sauce. The Applicant indicates that the professional can then add other additives that are involved in the usual composition of a coating dressing, such as biocides, antifoaming agents, optical brighteners and optical brightener supports, however this list is not exhaustive. Therefore, the process for manufacturing the coating sauce is also characterized in that it is also possible to use at least one water retaining agent and / or thickener other than the comb-type polymer used.

The process according to the invention is also characterized in that the mineral matter is chosen from natural or synthetic calcium carbonate, dolomites, kaolin, talc, gypsum, titanium oxide, satin white or even aluminum trihydroxide, the mica, the carbon black and the mixture of these charges between them, such as talc-calcium carbonate, calcium carbonate-kaolin mixtures, or even mixtures of calcium carbonate with aluminum trihydroxide, or even mixtures with synthetic or natural fibers or even the structures of minerals such as talc-calcium carbonate or talc-titanium dioxide. The mineral matter is preferably chosen from natural or synthetic calcium carbonate, kaolin, talc and mixtures of these fillers. The mineral matter is very preferably a mineral filler which is a natural or synthetic calcium carbonate or its mixtures. The mineral material is extremely preferably a natural calcium carbonate selected from marble, calcite, chalk or mixtures thereof. The process according to the invention is also characterized in that the binder is chosen from water-soluble binders and in particular starch, or from synthetic latex polymer binders such as styrene-based binders. acrylic and styrene-butadiene or their mixtures, or mixtures of these binders. The process according to the invention is also characterized in that the comb-type polymers have a molecular weight called Mw included between 100,000 g / mol and ,000,000 g / mol, preferably between 1,000,000 g / mol and 7,000,000 g / mol. The Applicant indicates that in the present Application, the molecular weight of the polymers used is determined according to the GPC method (Gel Phase Chromatography or Gel Permeability Chromatography) which uses a Waters ™ liquid chromatography apparatus equipped with two detectors, one of which combines the dynamic diffusion of the light to the viscosity measured by a Viscotek ™ viscometer and the other being a detector of Waters ™ brand refractometric concentration. This liquid chromatography apparatus is provided with steric exclusion columns suitably chosen by the professional in order to separate the different molecular weights of the polymers studied. The liquid phase of elution is an aqueous phase. In detail, 1 ml of the polymerization solution that is placed on a dish is removed, and then it is evaporated at room temperature under a vacuum of less than 1 mm of mercury. The solute is diluted to 0.9% in the eluent of the GPC, and the set is subsequently injected into the GPC device. The eluent of the GPC is a solution of NaHCO3: 0.08 mol / l, NaN03: 0.1 mol / l, triethanolamine: 0.02 mol / l, NaN3 0.03% mass. The GPC column contains an isocratic pump (Waters 515) whose flow rate is set at 0.5 ml / min, a furnace containing a "Guard Column Ultrahydrogel Waters ™" guard column, a 30 cm "Ultrahydrogel Waters ™" linear column long and 7.8 mm inner diameter and a refractometric detector type Rl Waters ™ 410. The furnace is heated up to the temperature of 60 ° C, and the refractometer is heated up to the temperature of 50 ° C. The GPC apparatus is calibrated by a series of 5 sodium polyacrylate standards supplied by Polymer Standard Service, and with a polimolecularity index included between 1.4 and 1.7, as well as with a sodium polyacrylate with a polymolecularity index equal to 2.4 and weight molecular weight equal to 5,600 g / mol. The process according to the invention is also characterized in that the comb-type polymers contain at least one monomer of formula (I): : D wherein: -myp represents a number of alkylene oxide portions less than or equal to 150, n represents a number of ethylene oxide portions less than or equal to 150, q represents an integer number at least equal to 1 and such as 5 < (m + n + p) q < 150, Ri represents the hydrogen or the methyl or ethyl radical, R 2 represents the hydrogen or the methyl or ethyl radical, - R represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of the vinyls as well as to the group of the esters acrylic, methacrylic, maleic, itaconic, crotonic, vinylphthalic as well as the group of unsaturated urethanes such as for example acryl urethane, methacryl urethane, aa'dimethyl-isopropenyl-benzylurethane, allyl urethane, as well as the group of allyl or vinyl ethers substituted or unsubstituted, or even the group of amides or ethylenically unsaturated imides, R 'represents hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms, or an ionizable or ionizable group such as a phosphate, a phosphonate, a sulfate, a sulfonate, a carboxylic, or even a primary, secondary or tertiary amine, or a quaternary ammonium, or even mixtures thereof.

The process according to the invention is also characterized in that the comb-type polymers are composed of: (a) of at least one anionic and carboxylic or dicarboxylic or phosphoric or phosphonic or sulphonic monomer or its mixture, (b) of at least one nonionic monomer, the nonionic monomer of at least one monomer of formula ( I): wherein: - m and p represent a number of portions of alkylene oxide less than or equal to 150, - n represents a number of portions of ethylene oxide less than or equal to 150, - q represents an integer number at least equal to 1 and such as 5 < (m + n + p) q < 150, and preferably such as 15 = (m + n + p) q < R 1 represents the hydrogen or the methyl or ethyl radical, - R 2 represents the hydrogen or the methyl or ethyl radical, - R represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of vinyl as well as the group of esters acrylic, methacrylic, maleic, itaconic, crotonic, vinylphthalic as well as the group of unsaturated urethanes such as for example acryl urethane, methacryl urethane, aa 'dimethyl-isopropenyl-benzylurethane, allyl urethane, as well as the group of allyl or vinyl ethers substituted or unsubstituted, or even the group of amides or ethylenically unsaturated imides, -R 'represents hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms, or an ionic or ionizable grouping as a phosphate, a phosphonate, a sulfate, a sulfonate, a carboxylic, or even a primary, secondary or tertiary amine, or a quaternary ammonium, or even their mixtures, and preferably represents a hydrocarbon radical having from 1 to 12 carbon atoms. carbon and most preferably a hydrocarbon radical having from 1 to 4 carbon atoms, or from the mixture of several monomers of formula (I), (c) optionally from the a monomer of the acrylamide or methacrylamide type or derivatives thereof such as N- [3- (dimethylamino) propyl] acrylamide or N- [3- (dimethylamino) propyl] methacrylamide, and mixtures thereof, or even at least one monomer non-water-soluble such as alkyl acrylates or methacrylates, unsaturated esters such as N- [2- (dimethylamino) ethyl methacrylate], or N- [2- (dimethylamino) ethyl acrylate], vinyls such as vinyl, vinylpyrrolidone, styrene, alphamethylstyrene and its derivatives, or at least one cationic monomer or quaternary ammonium such as chloride or [2- (methacryloyloxy) ethyl] trimethylammonium sulfate, chloride or sulfate [2- (acryloyloxy) ethyl] trimethylammonium, [3- (acrylamido) propyl] trimethylammonium chloride or sulfate, dimethyldiallylammonium chloride or sulfate, [3- (methacrylamido) propyl] trimethylammonium chloride or sulfate, or even of at least one organofluorinated or organosilylated monomer, or of the mixture of several of these monomers, (d) optionally of at least one monomer possessing at least two ethylenic unsaturations referred to in the continuation of the crosslinking monomer application. The process according to the invention is also characterized in that the comb-type polymer is constituted: (a) of at least one anionic monomer of ethylenic unsaturation and of monocarboxylic function selected from the monomers of ethylenic unsaturation and of monocarboxylic function such as acrylic or methacrylic acid or even the half esters of diacids such as the monoesters in Ci to C of the maleic or itaconic acids, or their mixtures, or chosen from the monomers of ethylenic unsaturation and dicarboxylic function such as crotonic, isocrotonic, cinnamic, itaconic, maleic, or even the anhydrides of carboxylic acids, such as maleic anhydride or chosen from the ethylenically unsaturated and sulphonic unsaturation monomers such as acrylamido-methylpropanesulfonic acid, sodium methallylsulfonate, vinylsulfonic acid and styrenesulfonic acid or even chosen from ethylenically unsaturated monomers and phosphoric function such as vinylphosphoric acid, ethylene glycol methacrylate phosphate, propylene glycol methacrylate phosphate, ethylene glycol acrylate phosphate, propylene glycol acrylate phosphate and its ethoxylates or even chosen among the monomers of ethylenic and functional unsaturation phosphonic acid such as vinylphosphonic acid, or mixtures thereof, (b) of at least one non-ionic ethylenic unsaturation monomer of formula (I): (I) in which: m and p represent a number of portions of alkylene oxide less than or equal to 150, n represents a number of portions of ethylene oxide less than or equal to 150, - q represents an integer at least equal to 1 and such as 5 < (m + n + p) q < 150, and preferably such as 15 < (m + n + p.) q <120, Ri represents the hydrogen or the methyl or ethyl radical, R 2 represents the hydrogen or the methyl or ethyl radical, R represents a radical containing a polymerizable unsaturated function, preferably belonging to the vinyl group as well as the acrylic, methacrylic, maleic, itaconic, crotonic, vinylphthalic group as well as the group of unsaturated urethanes such as acryl urethane, methacrylurethane, aa 'dimethyl-isopropenyl-benzylurethane, allyl urethane, as well as the group of the allylic or vinyl substituted or non-substituted ethers, or even the group of the amides or the ethylenically unsaturated imides, -R 'represents the hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms, or a group ionic or ionizable such as a phosphate, a phosphonate, a sulfate, a sulfonate, a carboxylic, or even a primary, secondary or tertiary amine, or a quaternary ammonium, or even their mixtures as, and preferably represents a hydrocarbon radical having from 1 to 12 carbon atoms and most preferably a hydrocarbon radical having from 1 to 4 carbon atoms, or from the mixture of several monomers of formula (I), (c) optionally of at least one monomer of the acrylamide or methacrylamide type or its derivatives such as N- [3- (dimethylamino) propyl] acrylamide or N- [3- (dimethylamino) propyl] methacrylamide, and mixtures thereof, or else at least one non-water-soluble monomer such as alkyl acrylates or methacrylates, unsaturated esters such as methacrylate N- [2- (dimethylamino) ethyl], or N- [2- (dimethylamino) ethyl acrylate], vinyls such as vinyl acetate, vinylpyrrolidone, styrene, alphamethylstyrene and their derivatives, or at least a cationic monomer or quaternary ammonium such as [2- (methacryloyloxy) ethyl] trimethylammonium chloride or sulfate, [2- (acryloyloxy) ethyl] trimethylammonium chloride or sulfate, [3- (acrylamido ) propyl] trimethylammonium, dimethyldiallylammonium chloride or sulfate, [3- (methacrylamido) propyl] trimethylammonium chloride or sulfate, or even at least one organofluorinated monomer, or even at least one organosilylated monomer selected preferably between the formulas molecules the (lia) or (Ilb) with the formula (lia) in which: - mi, pi, m2 and p2 represent a number of portions of alkylene oxide less than or equal to 150, - ni and n2 represent a number of ethylene oxide portions less than or equal to 150, Qi Y 2 represent an integer at least equal to 1 and such as 0 < (m? + n? + p?) qx < 150 and 0 < (m2 + n2 + p2) q2 < 150, - r represents a number such as 1 < r < 200, R represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of vinyl as well as to the group of acrylic esters, methacrylic, maleic, itaconic, crotonic, vinylphthalic as well as the group of unsaturated urethanes such as, for example, acryl urethane, methacrylurethane, aa'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as the group of allylic or vinyl ethers substituted or not , or even the group of amides or ethylenically unsaturated imides, R, R5, Rio and Rn, represent the hydrogen or the methyl or ethyl radical, R6, R7, R8 and R9, represent linear or branched alkyl, or aryl, groups , or alkylaryl, or arylalkyl having from 1 to 20 carbon atoms, or their mixture, - Ri2 represents a hydrocarbon radical having from 1 to 40 carbon atoms, A and B are possibly present groupings, which then represent a hydrocarbon radical which has 1 to 4 carbon atoms, with the formula (Ilb) R - A - Si (0B) 3 in which: R represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of the vinyls as well as to the group of the esters acrylic, methacrylic, maleic, itaconic, crotonic, vinylphthalic as well as the group of unsaturated urethanes such as, for example, acryl urethane, methacrylurethane, aa'dimethyl-isopropenyl-benzylurethane, allylurethane, and the group of allyl or vinyl ethers substituted or unsubstituted, or even the group of the amides or the ethylenically unsaturated imides, A is a possibly present group, which then represents a hydrocarbon radical having 1 to 4 carbon atoms, B represents a hydrocarbon radical having 1 to 4 carbon atoms, or mixture of several of these monomers, (d) optionally of at least one crosslinking monomer selected in a non-limiting manner from the group consisting of the dimethacrylate of tilenglicol, trimethylolpropane triacrylate, allyl acrylate, allyl maleates, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetralyloxyethane, triallylcyanurates, the allylic ethers obtained from polyols such as pentaerythritol, sorbitol, sucrose or others, or chosen from the molecules of formula (III): (III) in which: m3, p3, m4 and p4 represent a number of alkylene oxide portions less than or equal to 150, n3 and n4 represent a number of portions of ethylene oxide less than or equal to 150, - q3 and q4 represent an integer at least equal to 1 and such as 0 < (m3 + n3 + p3) q3 < 150 and 0 < (m4 + n4 + p4) q4 < 150, - r 'represents a number such as 1 < r '< 200, R? represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of vinyl as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic, vinylphthalic esters as well as to the group of unsaturated urethanes such as, for example, acryl urethane, methacrylurethane , aa 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as the group of allyl or vinyl ethers substituted or unsubstituted, or even the group of the amides or the ethylenically unsaturated imides, R14, R15, R20 and R2 ?, represent the hydrogen or the methyl or ethyl radical, - R? 6, R17 R? Y Ri9? represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having 1 to 20 carbon atoms, or their mixture, D and E are optionally present groupings, which then represent a hydrocarbon radical having from 1 to 4 atoms carbon, or the mixture of several of these monomers. The process according to the invention is also characterized in that the comb-type polymer is constituted, expressed by weight: (a) from 2% to 95% and even more in particular from 5% to 90% of at least one anionic monomer of ethylenic unsaturation and monocarboxylic function chosen from monomers of ethylenic unsaturation and monocarboxylic unsaturation such as acrylic or methacrylic acid, or even hemiesters of diacids such as monoesters in Ci to C4 of maleic or itaconic acids, or mixtures thereof, or chosen from monomers of ethylenic unsaturation and dicarboxylic function such as crotonic, isocrotonic, cinnamic, itaconic, maleic acid, or even the anhydrides of carboxylic acids, such as maleic anhydride or chosen from the monomers of ethylenic and sulfonic function unsaturation such as acrylamido-methylpropanesulfonic acid, sodium methallylsulfonate, vinylsulfonic acid and styrenesulfonic acid or even chosen from ethylenically unsaturated and phosphorus-functional monomers such as vinylphosphoric acid, ethylene glycol methacrylate phosphate , propylene glycol methacrylate phosphate, ethylene glycol acrylate phosphate, propylene glycol acrylate phosphate and its ethoxylates or even chosen from monomers of ethylenic unsaturation and phosphonic unsaturation such as vinylphosphonic acid, or mixtures thereof, (b) from 2% to 95% and even more in particular from 5% to 90% of at least one non-ionic ethylenic unsaturation monomer of formula (I). wherein: and p represent a number of alkylene oxide portions less than or equal to 150, n represents a number of portions of ethylene oxide less than or equal to 150, - q represents an integer at least equal to 1 and such as 5 < (m + n + p) q < 150, and preferably such as 15 < (m + n + p) q < 120, Ri represents the hydrogen or the methyl or ethyl radical, - R represents the hydrogen or the methyl or ethyl radical, R represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of the vinyls as well as to the group of the esters acrylic, methacrylic, maleic, itaconic, crotonic, vinylphthalic as well as the group of unsaturated urethanes such as acryl urethane, methacrylurethane, aa 'dimethyl-isopropenyl-benzylurethane, allyl urethane, and the group of allyl or vinyl ethers substituted or not , or even the group of amides or ethylenically unsaturated imides, R 'represents hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms, or an ionic or ionizable grouping such as a phosphate, a phosphonate, a sulfate , a sulfonate, a carboxylic, or even a primary, secondary or tertiary amine, or a quaternary ammonium, or even their mixtures, and represents preferably a hydrocarbon radical having from 1 to 12 carbon atoms and most preferably a hydrocarbon radical having from 1 to 4 carbon atoms, or of the mixture of several monomers of formula (I), (c) from 0% to 50% of at least one monomer of the acrylamide or methacrylamide type or its derivatives such as N- [3- (dimethylamino) propyl] acrylamide or N- [3- (dimethylamino) propyl] methacrylamide, and mixtures thereof, or even at least one non-water-soluble monomer such as alkyl acrylates or methacrylates, unsaturated esters such as N- [2- (dimethylamino) methacrylate ethyl], or the acrylate N- [2- (dimethylamino) ethyl], vinyl compounds such as vinyl acetate, vinylpyrrolidone, styrene, alphamethylstyrene and its derivatives, or at least one cationic monomer or quaternary ammonium such as chloride or sulphate [2] - (methacryloyloxy) ethyl] trimethylammonium, [2- (acryloyloxy) ethyl] trimethylammonium chloride or sulphate, [3- (acrylamido) propyl] trimethylammonium chloride, di-ethylodiallylammonium chloride or sulfate, chloride or [3- (methacrylamido) propyl] trimethylammonium sulfate, or even an organofluorinated monomer, or even an organosilylated monomer preferably chosen from the molecules of formulas (lia) or (Ilb): with the formula (lia) wherein: i, pi, m2 and p2 represent a number of alkylene oxide portions less than or equal to 150, ni and n2 represent a number of ethylene oxide portions less than or equal to 150, Pi Y P2 represent a number integer at least equal to 1 and such as 0 < (irti + ni + i) qi < 150 and 0 < (m2 + n2 + p2) q2 < 150, r represents a number such as 1 < r < 200, R3 represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of vinyl as well as to the group of esters acrylic, methacrylic, maleic, itaconic, crotonic, vinylphthalic and also to the group of unsaturated urethanes such as, for example, acryl urethane, methacrylurethane, aa'dimethyl-isopropenyl-benzylurethane, allylurethane, and the group of allyl or vinyl ethers substituted or unsubstituted, or even the group of amides or ethylenically unsaturated imides, R4, R5, Rio and Rn, represent the hydrogen or the methyl or ethyl radical, Re, R, Rs and Rg, represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having from 1 to 20 carbon atoms, or their mixture, R12 represents a hydrocarbon radical having from 1 to 40 carbon atoms, A and B are possibly present groups, which then represent a hydrocarbon radical having 1 to 4 carbon atoms, with the formula (Ilb) R - A - Si (OB) 3 in which: R represents a radical containing a polymerizable unsaturated function, belonging preferably to the group of vinyl as well as to the group of esters acrylic, methacrylic, maleic , itaconic, crotonic, vinylphthalic as well as the group of unsaturated urethanes such as acryl urethane, methacrylurethane, aa'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as the group of allyl or vinyl ethers substituted or not, or even the group of the amides or of the ethylenically unsaturated imides, A is a group optionally present, which then represents a hydrocarbon radical having 1 to 4 carbon atoms, B represents a hydrocarbon radical having 1 to 4 carbon atoms, or the mixture of several of these monomers, (d) from 0% to 3% of at least one crosslinking monomer chosen in a non-limiting manner from the group consisting of the dimethacrylate of tilenglicol, the triacrylate trimethylolpropane, allyl acrylate, allyl maleates, methylene-bis-acrylamide, methylene-bis-ethacrylamide, tetralyloxyethane, triallyl cyanurates, allyl ethers obtained from polyols such as pentaerythritol, sorbitol, sucrose or others, or chosen among the molecules of formula (III): (e) (III) in which: m3, p3, m4 and p4 represent a number of alkylene oxide portions less than or equal to 150, n and n4 represent a number of ethylene oxide portions less than or equal to 150, q3 and q represent a integer at least equal to 1 and such as 0 < (m3 + n3 + p3) q3 < 150 and 0 < (m4 + n + p4) q4 < 150, - r 'represents a number such as 1 < r '< 200, - R 3 represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of vinyl as well as to the group of acrylic, methacrylic, maleic, itaconic, crotonic, vinylphthalic esters as well as to the group of unsaturated urethanes such as, for example, acryl urethane, methacryl urethane, aa'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as the group of allylic or vinyl ethers substituted or unsubstituted, or even the group of amides or ethylenically unsaturated imides, R14, R? 5 / R2o and R2 ?, represent the hydrogen or the methyl or ethyl radical, R6, R17, Ri8 and R19, represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having from 1 to 20 carbon atoms; carbon, or its mixture, D and E are possibly present groups, which then represent a hydrocarbon radical having 1 to 4 carbon atoms, or of the mixture of several of these monomers, the total of the proportions of the components being equal a), b), c), and d) 100%. The polymer used according to the invention is obtained by known processes of root copolymerization in solution, in direct or inverse emulsion, in suspension or precipitation in appropriate solvents, in the presence of known catalytic systems and transfer agents, or even by processes of root polymerization controlled as the method called Fragmentation Transfer and Reversible Addition (RAFT), the method called Radical Polymerization with Transfer of Atoms (ATRP), the method called Nitroxide Mediated Polymerization (NMP) or even the method called Free Radical Polymerization Mediated by Cobaloxime. This polymer obtained in acidic and possibly distilled form can also be partially or totally neutralized by one or more neutralizing agents having a monovalent neutralizing function or a polyvalent neutralizing function such as, for example, for the monovalent function, those selected from the group consisting of alkali cations, in particular sodium, potassium, lithium, ammonium or primary, secondary or tertiary aliphatic and / or cyclic amines such as, for example, stearylamine, ethanolamines (mono-, di-, triethanolamine), mono- and diethylamine, cyclohexylamine, methylcyclohexylamine, aminomethylpropanol, morpholine, or even for polyvalent function, those selected from the group consisting of alkaline earth divalent cations, in particular magnesium and calcium, or even zinc, as well as trivalent cations, and in particular aluminum, or even some valence cations more ele vada. Each neutralization agent then intervenes according to percentages of neutralization specific to each valence function. According to another variant, the polymer from the The polymerization reaction can optionally before or after the total or partial neutralization reaction, be treated and separated into several phases, according to static or dynamic processes known to the practitioner, by one or more polar solvents belonging in particular to the group constituted by water , methanol, ethanol, propanol, isopropanol, butanols, acetone, tetrahydrofuran or their mixtures. One of the phases then corresponds to the polymer used according to the invention. According to another variant, the polymer can be dried. Another object of the invention lies in the coating sauces obtained by the process according to the invention. The last object of the invention is the use of the coating sauces according to the invention for coating paper and cardboard. The scope and interest of the invention will be better perceived thanks to the following examples that are not limiting. EXAMPLES Example 1 This example illustrates the process for manufacturing coating sauces according to the invention, a sauce in which a comb-like polymer obtained by grafting at least one function of polyalkylene oxide is directly introduced in the form of an aqueous solution. on the polymer chain, resulting in the polymerization chain of at least one ethylenic unsaturated monomer. Manufacture of coating sauces For each of the tests No. 1 to 7, a coating dressing is made by mixing: - 100 parts by dry weight of an aqueous suspension of calcium carbonate which is Norwegian marble and which is marketed by the OMYA ™ company under the name of Hydrocarb ™ 90, and whose dry weight content of calcium carbonate is equal to 78% of the total weight of the suspension; 10 parts by dry weight of styrene-butadiene latex marketed by DOW ™ CHEMICALS under the name DL 966, per 100 parts by dry weight of calcium carbonate; a certain amount of the polymer to be tested (according to the invention or according to the prior art), this amount being expressed in parts by dry weight of polymer, per 100 parts by dry weight of calcium carbonate. A coated sauce is thus obtained for which the dry weight content is set at 69% of the total weight of the sauce. Brookfield ™ viscosity measurement For each of the sauces thus formulated, the Brookfield ™ viscosity measurement at 100 revolutions per minute called μioo is first performed at 25 ° C according to the method well known to the manufacturer. professional Measurement of water retention Next, a water retention value is determined for each sauce, according to the following method. The water retention is determined thanks to an apparatus of the AAGWR type marketed by the company GRADEK ™. This apparatus is constituted by a measuring chamber in which a test paper called "Test Blotter Paper" is placed, covered by a perforated plastic cloth called "Test Filter PCTE", being the paper and the fabric marketed by the company GRADEK ™. Subsequently, 10 ml of the coating sauce to be tested is introduced into the chamber. The AAGWR device allows to exert a certain pressure on the coating sauce, driving all or part of the water and the water-soluble substances contained in the sauce, to pass through the perforated plastic cloth and to migrate to the test paper. Specifically, a pressure of 0.5 bar is applied for 90 seconds. The difference between the weight of the test paper before the Po experiment, and after the Pi experiment, provides the weight of water and the water-soluble substances contained in the coating sauce and that have migrated to the test paper along the length of the test paper. the experience . Specifically, a relative value of water retention increase is determined equal to: (Pi - P0) / P0. This value is determined when no polymer is used in the coated sauce: R? = L (Pl - Po) / Po] amount of polymer = 0 For each of the polymers used, the relative value of increase in water retention is determined, based on the amount of polymer x used: Rx = L ( Pl _ P?) / Po] amount of polymer = x It is represented, for an amount x of polymer used: R% = (Rx - R0) / Ro * 100 as a function of Brookfield viscosity μioo- Test n ° 1 East The test illustrates the prior art and uses a carboxymethylcellulose marketed by the company HUBER ™ under the name of Finnfix ™ 10, in a ratio equal to, expressed as parts of dry CMC per 100 parts by dry weight of calcium carbonate: - 0.2 for the Test 1-a-0.45 for the 1-b-0.7 test for the 1-c test. Test No. 2 This test illustrates the prior art and uses a copolymer of methacrylic acid and ethyl acrylate, in a ratio equal to, expressed in parts by dry weight of copolymer per 100 parts by dry weight of calcium carbonate: - 0.2 for the 2-a-0.3 test for the 2-b-0.55 test for the 2-c test. Test No. 3 This test illustrates the invention and uses a polymer consisting of, expressed as a percentage by weight of the monomers: - 5.9% acrylic acid - 1.6% methacrylic acid - 92.5% methoxypolyethylene glycol methacrylate of molecular weight equal to 5,000 g / mol, the polymer having a molecular weight equal to 2,560,000 g / mol. This polymer is used in a ratio equal to, expressed in parts by dry weight of polymer per 100 parts by dry weight of calcium carbonate: - 0.3 for the 3-to-0.8 test for the 3-b-1.2 test for the test 3-c-3.0 for the 3-d assay. Test No. 4 This test illustrates the invention and uses a polymer consisting of, expressed as a percentage by weight of the monomers: - 5.9% acrylic acid - 1.6% methacrylic acid 92.5% methoxypolyethylene glycol methacrylate of molecular weight equal to 5,000 g / mol, the polymer having a molecular weight determined by GPC equal to 950,000 g / mol. This polymer is used in a ratio equal to, expressed in parts by dry weight of polymer per 100 parts by dry weight of calcium carbonate: - 0.3 for the 4-a-0.8 test for the 4-b-1.2 test for the test 4-c. Test No 5 This test illustrates the invention and uses a polymer consisting of, expressed in weight percentage of the monomers: - 5.9% acrylic acid - 1.6% methacrylic acid 92.5% methoxypolyethylene glycol methacrylate of molecular weight equal to 5,000 g / mol having the polymer a molecular weight equal to 4,350,000 g / mol. This polymer is used in a proportion equal to, expressed in parts by dry weight of polymer per 100 parts by dry weight of calcium carbonate: - 0.3 for the 5-a test - 0.8 for the 5-b - 1.2 test for the 5-c test. For each of the tests n ° 5, the values of the Brookfield ™ viscosity measured at 25 ° C and at 100 revolutions per minute (μioo) as well as the relative increase in water retention (R) are given in Table 1 On the other hand, it is indicated that the value of μioo is equal to 112 mPa.s for the sauce that does not contain any additive, and that the value of the water retention Pi - Po is equal to 239 grams for this same sauce that It does not contain any additives.

Table 1: Brookfield ™ viscosity measured at 25 ° C and at 100 revolutions per minute (μioo) and relative increase in water retention (R%). These results were represented in figure 1.

Examination of this figure clearly demonstrates that the use of the comb-like polymers according to the invention makes it possible to improve the Brookfield ™ water / viscosity holding pair, ie to obtain: - for a given Brookfield ™ viscosity, improved water retention (more high) that with the use of a prior art water retaining thickener in the coating dressing, or for a given water retention, an improved (lower) Brookfield ™ viscosity than with a prior art water retaining thickener in the coated sauce. EXAMPLE 2 This example illustrates the process for the manufacture of coating sauces according to the invention, sauces into which a comb-like polymer, obtained by grafting at least one polyalkylene oxide function on top, is directly introduced in the form of an aqueous solution. the polymer chain, resulting in the polymerization chain of at least one ethylenic unsaturated monomer. Manufacture of coating sauces For each of the tests Nos. 6 to 14, a coating dressing is made by mixing: 100 parts by dry weight of an aqueous suspension of calcium carbonate which is Norwegian marble and which is marketed by the company OMYA ™ under the name Hydrocarb ™ 90, and whose dry weight content of calcium carbonate is equal to 78% of the total weight of the suspension; 11 parts by dry weight of styrene-butadiene latex marketed by DOW ™ CHEMICALS under the name of DL 966, per 100 parts by dry weight of calcium carbonate; 0.4 parts by dry weight of polyvinyl alcohol per 100 parts by dry weight of calcium carbonate; - 1 part by dry weight of optical brightener marketed by the company BAYER ™ with the name of Blancophor ™ P, per 100 parts by dry weight of calcium carbonate; the polymer to be tested (according to the invention or according to the prior art), in 2 amounts equal to 0.4 and 0.6 parts by dry weight of the polymer, per 100 parts by dry weight of calcium carbonate. In this way, a coating sauce is obtained for which the content in dry weight is set at 68% of the total weight of the sauce. Measurement of Brookfield ™ viscosity For each of the sauces thus formulated, the Brookfield ™ viscosity measurement at 100 revolutions per minute denoted μioo is first performed at 25 ° C according to the method well known to the professional.

Measurement of water retention A water retention value is then determined for each sauce, according to the method described in example 1. Test No. 6 This test illustrates the prior art and uses a carboxymethyl cellulose marketed by METSA SERLA ™. under the name of Finnfix ™ 10. Test n ° 7 This test illustrates the invention and a polymer consisting of, expressed in weight percentage of the monomers is used: - 5.9% acrylic acid - 1.6% methacrylic acid 92.5% methacrylate of methoxypolyethylene glycol of molecular weight equal to 5,000 g / mol, the polymer having a molecular weight equal to 2,560,000 g / mol. Test n ° 8 This test illustrates the invention and a polymer consisting of, expressed in weight percentage of the monomers is used: - 6.0% acrylic acid 94% methoxypolyethylene glycol methacrylate of molecular weight equal to 750 g / mol having the polymer a molecular weight equal to 1,574,000 g / mol.

Test n ° 9 This test illustrates the invention and a polymer consisting of, expressed in weight percentage of the monomers is used: - 6% acrylic acid 94% methoxypolyethylene glycol methacrylate of molecular weight equal to 2,000 g / mol having the polymer a molecular weight equal to 2,085,000 g / mol. Test No. 10 This test illustrates the invention and a polymer consisting of, expressed as a percentage by weight of the monomers is used: - 30% acrylic acid - 70% methoxypolyethylene glycol methacrylate of molecular weight equal to 5,000 g / mol having the polymer a molecular weight equal to 60,000 g / mol.

Test No. 11 This test illustrates the invention and a polymer consisting of, expressed in weight percentage of the monomers is used: - 40% acrylic acid 60% methoxypolyethylene glycol methacrylate of molecular weight equal to 5,000 g / mol having the polymer a molecular weight equal to 67,000 g / mol.

Test No. 12 This test illustrates the invention and a polymer consisting of, expressed in weight percentage of the monomers is used: - 5.0% acrylic acid - 2.6% acrylamido-methylpropanesulfonic acid 92.4% methoxypolyethylene glycol methacrylate of equal molecular weight to 5,000 g / mol having the polymer a molecular weight equal to 460,000 g / mol. Test No. 13 This test illustrates the invention and a polymer consisting of, expressed in weight percentage of the monomers is used: - 15.6% ethylene glycol methacrylate phosphate 84.4% methoxypolyethylene glycol methacrylate of molecular weight equal to 5,000 g / mol the polymer having a molecular weight equal to 2,560,000 g / mol. Test No. 14 This test illustrates the invention and a polymer consisting of, expressed in weight percentage of the monomers is used: - 6.0% acrylic acid 94.0% methoxypolyethylene glycol methacrylate of molecular weight equal to 3,000 g / mol having the polymer a molecular weight equal to 2,560,000 g / mol. As for example 1, it is represented, for a quantity x (here equal to 0, 0.4 and 0.6 parts by dry weight of the polymer per 100 parts of calcium carbonate) of polymer used: R% = (Rx - Ro) / Ro * 100 as a function of Brookfield viscosity μioo • This representation is shown in Figure 2. Examination of this figure clearly demonstrates that the use of the comb-like polymers according to the invention allows the Brookfield ™ water / viscosity retention pair to be improved, ie to obtain: for a given Brookfield ™ viscosity, improved water retention (higher) than with the use of a prior art water retaining thickener in the coating dressing, - or for a given water retention, an improved (lower) Brookfield ™ viscosity than with a Thickening agent water retainer prior art in the coating sauce. EXAMPLE 3 This example illustrates the process for manufacturing coating sauces according to the invention, a sauce in which a comb-type polymer is introduced, obtained by grafting at least one polyalkylene oxide function onto the polymer chain, resulting in the chain the polymerization of at least one ethylenic unsaturated monomer. This polymer is introduced in the form of an aqueous dispersion of calcium carbonate, using the polymer to disperse the calcium carbonate in the water. Manufacture of coating sauces For each of the tests No. 15 to 17, a coating dressing is made by mixing: 100 parts by dry weight of an aqueous suspension of calcium carbonate which is a Norwegian marble, whose The dry weight content of calcium carbonate is equal to 78% of the total weight of the dispersion, and it contains a polymer that has served to grind or disperse the calcium carbonate, the polymer being a prior art polymer or the polymer according to the invention. invention; 11 parts by dry weight of styrene-butadiene latex marketed by DOW ™ CHEMICALS under the name of DL 966, per 100 parts by dry weight of calcium carbonate; 0.6 parts by dry weight of a carboxymethyl cellulose sold by the company METSA SERLA ™ under the name of Finnfix ™ 10; 0.3 parts by dry weight of polyvinyl alcohol, per 100 parts by dry weight of calcium carbonate; 0.5 parts by dry weight of optical brightener commercialized by the company BAYER ™ with the name of Blancophor ™ P, per 100 parts by dry weight of carbonate of calcium,-. In this way, a coating sauce is carried out for which the content in dry weight is set at 67% of the total weight of the sauce. Measurement of Brookfield ™ viscosity For each of the sauces thus formulated, the Brookfield ™ viscosity measurement at 100 revolutions per minute is first performed at 25 ° C, according to the method well known to the professional. Measurement of water retention A water retention value is then determined for each sauce, according to the method described in the example 1. Test No. 15 This test illustrates the prior art and uses 2% by dry weight of a homopolymer of acrylic acid with respect to the dry weight of calcium carbonate, to disperse calcium carbonate in water. Test n ° 16 This test illustrates the invention and uses 2% by dry weight of a polymer (with respect to the dry weight of calcium carbonate) constituted by, expressed in weight percentage of the monomers: - 5.9% acrylic acid - 1.6 % methacrylic acid 92. 5% methoxypolyethylene glycol methacrylate of molecular weight equal to 5,000 g / mol, the polymer having a molecular weight equal to 2,560,000 g / mol. This polymer has served to disperse calcium carbonate in water. Test No. 17 This test illustrates the invention and uses 2% by dry weight of a polymer (based on the dry weight of calcium carbonate) constituted by, expressed as a percentage by weight of the monomers: - 5.9% acrylic acid - 1.6 % methacrylic acid 92.5% methoxypolyethylene glycol methacrylate of molecular weight equal to 5,000 g / mol having the polymer a molecular weight equal to 2,560,000 g / mol. This polymer has served to grind calcium carbonate in water. The values of the Brookfield viscosity measured at 100 revolutions / minute and the water retention as indicated above, were indicated in table 2, as regards the coating sauces corresponding to the tests n ° 15 to 17 .

Table 3 The reading of Table 3 shows that, the polymers used according to the invention, allow reducing the Brookfield viscosity of the coating sauces, while improving their water retention. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (17)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. Process for manufacturing coating sauces containing: (a) at least one mineral material, (b) at least one binder, (c) water, characterized in that an agent which increases the water retention and reduces the Brookfield ™ viscosity of the composition, which consists of at least one comb-like polymer, obtained by grafting at least one of the composition, is introduced into the composition mentioned above. polyalkylene oxide function on the polymer chain, resulting in the polymerization chain of at least one ethylenic unsaturated monomer.
2. 2. The process according to claim 1, characterized in that the polymer is introduced: i. with the mineral material, in the form of dry powder, and / or aqueous dispersion and / or aqueous suspension resulting from the steps of: grinding and / or dispersion in wet and preferably aqueous medium of the mineral material in the presence of the polymer, and eventually in the presence of at least one agent of wet milling and / or of at least one dispersing agent, leading to the obtaining of a dispersion and / or of an aqueous suspension of the mineral matter; and in the case of dry powder only, of the drying of the dispersion and / or of the aqueous suspension of the mineral matter, and then optionally treatment and classification of the obtained powder; ii. and / or with the mineral material, in the form of aqueous dispersion and / or aqueous suspension, resulting from the steps of: dry grinding the mineral filler, optionally in the presence of at least one dry milling agent, then eventually treatment and classification of the obtained powder; dispersion and / or aqueous suspension of the powder obtained, with introduction of the polymer and possibly in the presence of a dispersing agent; iii. and / or with the mineral material in the form of dry powder, and / or aqueous dispersion and / or aqueous suspension resulting from the steps of: introducing the polymer into a dispersion and / or an aqueous suspension containing the material mineral; and in the case of dry powder only, of the drying of the dispersion and / or of the aqueous suspension of the mineral matter, and then optionally treatment and classification of the obtained powder; iv) and / or in the form of dry powder mixed with the other components a), b) and c); v) and / or in the form of an aqueous solution mixed with the other components a), b) and c).
3. The process according to one of claims 1 or 2, characterized in that the coating sauce contains, in percentage by weight of each component with respect to the total weight of the coating sauce: (a) from 3 parts to 20 parts , preferably from 5 parts to 15 parts by dry weight of binder, per 100 parts by dry weight of mineral matter, (b) from 0.1 parts to 2 parts, preferably from 0.1 to 1.5 parts by dry weight of comb-like polymer, 100 parts by dry weight of mineral matter, (c) water in an amount by weight included between 20% and 80%, with respect to the total weight of the coating sauce.
4. The process according to one of claims 1 to 3, characterized in that at least one water retaining agent and / or thickener other than the comb-type polymer used is also used.
5. The process according to one of claims 1 to 4, characterized in that the mineral matter is chosen from natural or synthetic calcium carbonate, dolomites, kaolin, talc, gypsum, titanium oxide, white satin or even trihydroxide aluminum, mica, carbon black and the mixture of these charges between them, such as mixtures of talc-calcium carbonate, calcium carbonate-kaolin, or even mixtures of calcium carbonate with aluminum trihydroxide, or even mixtures with synthetic or natural fibers or even the structures of minerals such as talc-calcium carbonate or talc-titanium dioxide structures, preferably chosen from natural or synthetic calcium carbonate, kaolin, talc and mixtures of these fillers, very preferably chosen from natural or synthetic calcium carbonate or its mixtures, and even more preferably chosen from marble, calcite , the chalk or its mixtures.
6. The process according to one of claims 1 to 5, characterized in that the binder is chosen from water-soluble binders and in particular starch, or from binders of synthetic latex polymers such as styrene-acrylics and styrene-butadienes or their mixtures, or the mixtures of these binders.
7. The process according to one of claims 1 to 6, characterized in that the comb-type polymers have a molecular weight designated Mw included between 100,000 g / mol and 10,000,000 g / mol, preferably between 1,000,000 g / mol and 7,000,000 g / mol. mol.
8. 8. The process according to one of claims 1 to 7, characterized in that the comb-type polymers contain at least one monomer of formula (I): (I) in which: - m and p represent a number of portions of alkylene oxide less than or equal to 150, n represents a number of portions of ethylene oxide less than or equal to 150, q represents an integer at least equal to 1 and such as 5 < (m + n + p) q < 150, Ri represents the hydrogen or the methyl or ethyl radical, R 2 represents the hydrogen or the methyl or ethyl radical, R represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of the vinyls as well as to the group of the acrylic esters , methacrylic, maleic, itaconic, crotonic, vinylphthalic and the group of unsaturated urethanes such as, for example, acryl urethane, methacrylurethane, aa'dimethyl-isopropenyl-benzylurethane, allylurethane, and also the group of allyl or vinyl ethers substituted or unsubstituted, or even the group of amides or ethylenically unsaturated imides, R 'represents hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms, or an ionizable or ionizable group such as a phosphate, a phosphonate, a sulfate, a sulfonate, a carboxylic, or even a primary, secondary or tertiary amine, or a quaternary ammonium, or even mixtures thereof.
9. The process according to one of claims 1 to 8, characterized in that the comb-type polymers are composed: (a) of at least one anionic and carboxylic or dicarboxylic or phosphoric or phosphonic or sulphonic monomer or its mixture, (b) of at least one nonionic monomer, the nonionic monomer of at least one monomer of formula (I) being constituted: wherein: - m and p represent a number of portions of alkylene oxide less than or equal to 150, - n represents a number of portions of ethylene oxide less than or equal to 150, - q represents an integer at least equal to 1 and such that 5 = (m + n + p) q < 150, and preferably such as 15 < (m + n + p) q < 120 - Ri represents the hydrogen or the methyl or ethyl radical, - R2 represents the hydrogen or the methyl or ethyl radical, - R represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of vinyl as well as to the group of esters acrylic, methacrylic, maleic, itaconic, crotonic, vinylphthalic as well as to the group of unsaturated urethanes such as for example acrylurethane , methacryl urethane, aa 'dimethyl-isopropenyl-benzylurethane, allyl urethane, and also the group of allyl or vinyl ethers substituted or unsubstituted, or even the group of amides or ethylenically unsaturated imides, - R' represents hydrogen or a radical hydrocarbon having from 1 to 40 carbon atoms, or an ionic or ionizable grouping such as a phosphate, a phosphonate, a sulfate, a sulfonate, a carboxylic, or even a primary, secondary or tertiary amine, or a quaternary ammonium, or even their mixtures, and preferably represents a hydrocarbon radical having from 1 to 12 carbon atoms and most preferably a hydrocarbon radical Onado that has 1 to 4 carbon atoms, or of the mixture of several monomers of formula (I), (c) optionally of at least one monomer of the acrylamide or methacrylamide type or its derivatives such as N- [3- (dimethylamino) propyl] acrylamide or N- [3- (dimethylamino) propyl] methacrylamide, and mixtures thereof, or even at least one non-water-soluble monomer such as alkyl acrylates or methacrylates, unsaturated esters such as N- [2- (dimethylamino) ethyl methacrylate], or N- [2- (dimethylamino) ethyl acrylate], vinylics such as vinyl acetate, vinylpyrrolidone, styrene, alphamethylstyrene and its derivatives, or at least one cationic monomer or quaternary ammonium such as chloride or sulphate [2- (methacryloyloxy) ethyl] trimethylammonium, [2- (acryloyloxy) ethyl] trimethylammonium chloride or sulfate, [3- (acrylamido) propyl] trimethylammonium chloride or sulfate, dimethyldiallylammonium chloride or sulfate, chloride or sulfate [3- (methacrylamido) propyl] trimethylammonium, or even at least one organofluorinated or organosilylated monomer, or of the mixture of several of these monomers, (d) optionally of at least one monomer possessing at least two ethylenic unsaturations.
10. The process according to one of claims 1 to 9, characterized in that the comb-type polymer is constituted: (a) of at least one anionic monomer of ethylenic unsaturation and monocarboxylic function selected from monomers of ethylenic unsaturation and of monocarboxylic function such as acrylic or methacrylic acid or even hemiesters of diacids such as monoesters in Ci to C4 of maleic or itaconic acids, or mixtures thereof, or chosen from unsaturation monomers ethylenic and dicarboxylic function such as crotonic, isocrotonic, cinnamic, itaconic, maleic, or even anhydrides of carboxylic acids, such as maleic anhydride or chosen from monomers of ethylenic and sulfonic function unsaturation such as acrylamido-methylpropanesulfonic acid, methallylsulfonate of sodium, vinylsulfonic acid and styrenesulfonic acid or even chosen from ethylenically unsaturated and phosphorus-functional monomers such as vinylphosphoric acid, ethylene glycol methacrylate phosphate, propylene glycol methacrylate phosphate, ethylene glycol acrylate phosphate, the fo propylene glycol acrylate sulfate and its ethoxylates or even chosen from ethylenically unsaturated and phosphonic unsaturation monomers such as vinylphosphonic acid, or mixtures thereof, (b) of at least one non-ionic ethylenic unsaturation monomer of formula (I): in which: m and p represent a number of alkylene oxide portions less than or equal to 150, n represents a number of ethylene oxide portions less than or equal to 150, - q represents an integer at least equal to 1 and such as 5 < (m + n + p) q < 150, and preferably such as 15 < (m + n + p) q < 120, Ri represents the hydrogen or the methyl or ethyl radical, - R2 represents the hydrogen or the methyl or ethyl radical, R represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of vinyl as well as to the group of esters acrylic, methacrylic, maleic, itaconic, crotonic, vinylphthalic as well as the group of unsaturated urethanes such as acryl urethane, methacrylurethane, aa 'dimethyl-isopropenyl-benzylurethane, allyl urethane, and the group of allyl or vinyl ethers substituted or not , or even the group of amides or ethylenically unsaturated imides, R 'represents hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms, or an ionic or ionizable grouping such as a phosphate, a phosphonate, a sulfate , a sulfonate, a carboxylic acid, or even a primary, secondary or tertiary amine, or a quaternary ammonium, or even their mixtures, and preferably represents a hydrocarbon radical having from 1 to 12 carbon atoms and most preferably a hydrocarbon radical having from 1 to 4 carbon atoms, or of the mixture of several monomers of formula (I), (c) optionally of at least one monomer of the acrylamide or methacrylamide type or its derivatives such as N- [3- (dimethylamino) propyl] acrylamide or N- [3- (dimethylamino) propyl] methacrylamide, and mixtures thereof, or even at least one non-water-soluble monomer such as alkyl acrylates or methacrylates, unsaturated esters such as N- [2- (dimethylamino) ethyl methacrylate], or N- [2- (dimethylamino) ethyl acrylate], vinylics such as vinyl acetate, vinylpyrrolidone, styrene, alphamethylstyrene and its derivatives, or at least one cationic monomer or quaternary ammonium such as chloride or sulphate [2- (methacryloyloxy ) ethyl] trimethylammonium, [2- (acryloyloxy) ethyl] trimethylammonium chloride or sulfate, [3- (acrylamido) propyl] trimethylammonium chloride or sulfate, dimethyldiallylammonium chloride or sulfate, chloride or sulfate of [3- (methacrylamido) propyl] trimethylammonium, or even at least one organofluorinated monomer, or even at least one organosilylated monomer selected preferably from the molecules of formulas (lia) or (Ilb) with the formula (lia) in which: - mi, pi, m2 and p2 represent a number of portions of alkylene oxide less than or equal to 150, - ni and n2 represent a number of portions of ethylene oxide less than or equal to 150, i and q2 represent a integer at least equal to 1 and such as 0 <; (irti + ni + pi) qi < 150 and 0 < (m2 + n2 + p2) q2 < 150, - r represents a number such as 1 < r < 200, R3 represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of vinyl as well as to the group of esters acrylic, methacrylic, maleic, itaconic, crotonic, vin-ilphthalic as well as to the group of unsaturated urethanes as per examples include acryl urethane, methacryl urethane, α-α 'dimethyl-isopropenyl-benzylurethane, allyl urethane, and also the group of allyl or vinyl ethers substituted or unsubstituted, or even the group of amides or ethylenically unsaturated imides, R4, R5, Rio and Rn, represent the hydrogen or the methyl or ethyl radical, R6, R7, R8 and R9, represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having from 1 to 20 carbon atoms , or its mixture, - R12 represents a hydrocarbon radical having from 1 to 40 carbon atoms, A and B are optionally present groups, which then represent a hydrocarbon radical having from 1 to 4 carbon atoms, with the formula (IIb) ) R - A - Si (OB) 3 in which: R represents a radical containing a polymerizable unsaturated function, belonging preferably to the group of vinyl as well as to the group of esters acrylic, methacrylic, maleic, itaconic, crotonic, vinylphthalic as well as the group of unsaturated urethanes such as, for example, acryl urethane, methacrylurethane, aa'dimethyl-isopropenyl-benzylurethane, allylurethane, and the group of allyl or vinyl ethers substituted or unsubstituted, or of the amides or of the ethylenically unsaturated imides, A is a possibly present group, which then represents a hydrocarbon radical having 1 at 4 carbon atoms, B represents a hydrocarbon radical having from 1 to 4 carbon atoms, or from the mixture of several of these monomers, (d) optionally from at least one crosslinking monomer chosen from the constituted group in a non-limiting manner by ethylene glycol dimethacrylate, trimethylolpropane triacrylate, allyl acrylate, allyl maleates, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetralyloxyethane, triallyl cyanurates, allyl ethers obtained from polyols such as pentaerythritol, sorbitol, sucrose or others, or chosen from the molecules of formula (III): (III) in which: m3, p3, m4 and p4 represent a number of alkylene oxide portions less than or equal to 150, n3 and n4 represent a number of portions of ethylene oxide less than or equal to 150, - q3 and q4 represent a whole number at least equal to 1 and such as 0 < (m3 + n3 + p3) q3 < 150 and 0 < (m4 + n4 + p4) q < 150, - r 'represents a number such as 1 < r '< 200, R? represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of vinyl as well as to the group of esters acrylic, methacrylic, maleic, itaconic, crotonic, vinylphthalic as well as to the group of unsaturated urethanes such as for example acryl urethane, methacrylurethane , aa 'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as the group of allylic or vinyl ethers substituted or unsubstituted, or even the group of amides or ethylenically unsaturated imides, Ri4, R15, R20 and 21 represent hydrogen or the methyl or ethyl radical, - Rie, R17, Rie and Ri9 represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having from 1 to 20 carbon atoms, or their mixture, D and E are groupings optionally present , which then represent a hydrocarbon radical having from 1 to 4 carbon atoms, or from the mixture of several of these monomers.
11. The process according to one of claims 1 to 10, characterized in that the comb-like polymer is constituted, expressed by weight: (a) from 2% to 95% and even more in particular from 5% to 90% of at least one anionic monomer of ethylenic unsaturation and monocarboxylic function chosen from monomers of ethylenic unsaturation and monocarboxylic unsaturation such as acrylic or methacrylic acid, or even hemiesters of diacids such as monoesters in Ci to C4 of maleic or itaconic acids , or mixtures thereof, or chosen from the monomers of ethylenic unsaturation and dicarboxylic function such as crotonic, isocrotonic, cinnamic, itaconic, maleic, or even carboxylic acid anhydrides, such as maleic anhydride or chosen from ethylenically unsaturated monomers and of sulfonic function such as acrylamido-methylpropanesulfonic acid, sodium methallylsulfonate, vinylsulfonic acid and styrenesulfonic acid or even chosen from ethylenically unsaturated and phosphoric unsaturation monomers such as vinylphosphoric acid, ethylene glycol methacrylate phosphate, propylene glycol methacrylate phosphate, acrylate phosphate of ethylene glycol, propylene glycol acrylate phosphate and its ethoxylates or even chosen from monomers of ethylenic unsaturation and phosphonic unsaturation such as vinylphosphonic acid, or mixtures thereof, (b) from 2% to 95% and even more in particular from 5% to 90% of at least one non-ionic ethylenic unsaturation monomer of formula (I): (I) in which: m and p represent a number of portions of alkylene oxide less than or equal to 150, n represents a number of portions of ethylene oxide less than or equal to 150, q represents an integer at least equal to 1 and such as 5 < (m + n + p) q < 150, and preferably such as 15 < (m + n + p) q < 120, Ri represents the hydrogen or the methyl or ethyl radical, R 2 represents the hydrogen or the methyl or ethyl radical, R represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of the vinyls as well as to the group of the acrylic esters , methacrylic, maleic, itaconic, crotonic, vinylphthalic as well as the group of unsaturated urethanes such as, for example, acryl urethane, methacryl urethane, aa'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as the group of allyl or vinyl ethers substituted or unsubstituted, or even the group of amides or ethylenically unsaturated imides, R 'represents hydrogen or a hydrocarbon radical having from 1 to 40 carbon atoms, or an ionizable or ionizable group such as a phosphate, a phosphonate, a sulfate, a sulfonate, a carboxylic, or even a primary, secondary or tertiary amine, or a quaternary ammonium, or even their mixtures, and preferably represents a hydrocarbon radical having 1 to 12 carbon atoms and most preferably a hydrocarbon radical having 1 to 12 carbon atoms; to 4 carbon atoms, or of the mixture of several monomers of formula (I), (c) from 0% to 50% of at least one monomer of the acrylamide or methacrylamide type or its derivatives such as N- [3- (dimethylamino propyl] acrylamide or N- [3- (dimethylamino) propyl] methacrylamide, and mixtures thereof, or even at least one non-water-soluble monomer such as alkyl acrylates or methacrylates, unsaturated esters such as N-methacrylate [2- (di methylamino) ethyl], or N- [2- (dimethylamino) ethyl acrylate], vinyls such as vinyl acetate, vinylpyrrolidone, styrene, alphamethylstyrene and its derivatives, or at least one cationic monomer or quaternary ammonium such as [2- (methacryloyloxy) ethyl] trimethylammonium chloride or sulfate, [2- (acryloyloxy) ethyl] trimethylammonium chloride or sulfate, chloride of [3- (acrylamido) propyl] trimethylammonium, dimethyldiallylammonium chloride or sulfate, [3- (methacrylamido) propyl] trimethylammonium chloride or sulfate, or even of an organofluorinated monomer, or even of an organosilylated monomer chosen from preferably between the molecules of formulas (lia) or (Ilb): with the formula (lia) wherein: mi, pi, m2 and p2 represent a number of alkylene oxide portions less than or equal to 150, ni and n2 represent a number of ethylene oxide portions less than or equal to 150, Pi Y q2 represent a number integer at least equal to 1 and such as 0 < (m? + n? + p?) q? < 150 and 0 < (m2 + n2 + p2) q2 < 150, - r represents a number such as 1 < r = 200, R3 represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of vinyl as well as to the group of the esters acrylic, methacrylic, maleic, itaconic, crotonic, vinylphthalic as well as the group of the unsaturated urethanes such as, for example, acryl urethane, methacryl urethane, aa'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as the group of allyl or vinyl ethers substituted or unsubstituted, or even the group of amides or ethylenically unsaturated imides, R4, R5, Rio and Rn, represent the hydrogen or the methyl or ethyl radical, R6, R7, R8 and R9, represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having from 1 to 20 carbon atoms, or their mixture , R 2 represents a hydrocarbon radical having from 1 to 40 carbon atoms, A and B are optionally present groupings, which then represent a hydrocarbon radical having from 1 to 4 carbon atoms, with the formula (Ilb) R - A - Si (OB) 3 in which: R represents a radical containing a polymerizable unsaturated function, preferably belonging to the group of vinyl as well as to the group of esters acrylic, methacrylic, maleic, itaconic, crotonic , vinylphthalic as well as the group of unsaturated urethanes such as, for example, acryl urethane, methacrylurethane, a-a'dimethyl-isopropenyl-benzylurethane, allylurethane, as well as A group of allylic or vinyl ethers substituted or unsubstituted, or even the group of amides or ethylenically unsaturated imides, A is a group optionally present, which then represents a hydrocarbon radical having 1 to 4 carbon atoms, B represents a hydrocarbon radical having from 1 to 4 carbon atoms, or from the mixture of several of these monomers, (d) from 0% to 3% of at least one crosslinking monomer selected from the group consisting of dimethacrylate in a non-limiting manner ethylene glycol, trimethylolpropane triacrylate, allyl acrylate, maleates allyl, methylene-bis-acrylamide, methylene-bis-methacrylamide, the tetrallyloxyethane, the triallylcyanurates, allylic ethers obtained from polyols such as pentaerythritol, sorbitol, sucrose or others, or chosen among the molecules of formula (III): : ni) in which m3, p3, m4 and p4 represent a number of alkylene oxide portions less than or equal to 150, n3 and n4 represent a number of ethylene oxide portions less than or equal to 150, - q3 and q4 represent a whole number at least equal to 1 and such as 0 < (m + n3 + p3) q3 < 150 and 0 < (m + n + p) q4 < 150, r 'represents a number such as 1 < r '< 200, R13 represents a radical containing one, belonging to group preferably vinyl and the group of acrylic, methacrylic, maleic, itaconic, crotonic, vinyl phthalic as well as the unsaturated urethanes group as polymerizable unsaturated function example acrylurethane, methacrylurethane, aa 'dimethyl-isopropenyl-benzylurethane, allylurethane, and to the group of allyl or vinyl ethers substituted or not, or to the group of amides or of the ethylenically unsaturated imides, Ri4, R15, R2O and R2i / represent the hydrogen or the methyl or ethyl radical, - Ri6, R17, Ri8 and i9 / represent linear or branched alkyl, or aryl, or alkylaryl, or arylalkyl groups having from 1 to 20 carbon atoms, or their mixture, D and E are possibly present groups, which then represent a hydrocarbon radical having 1 to 4 carbon atoms, or of the mixture of several of these monomers, the total of the proportions of components a), b), c), and d) being equal to 100%.
12. The process according to one of claims 1 to 11, characterized in that the comb-type polymer is obtained by processes of root copolymerization in solution, in direct or inverse emulsion, in suspension or precipitation in appropriate solvents, in the presence of systems and catalytic transfer agents known, or by processes root controlled polymerization as the method called transfer Fragmentation and Adding Reversible (RAFT), the method known radical polymerization atom transfer (ATRP), the method known polymerization Mediated Nitroxide (NMP) or even the method called Cobaloxime-mediated Free Radical Polymerization.
13. The process according to one of claims 1 to 12, characterized in that the comb-like polymer obtained in acidic and optionally distilled form can be partially or totally neutralized by one or more neutralizing agents that have a monovalent neutralizing function. or of a polyvalent neutralizing function as for the monovalent function of the elect of the group constituted by the alkaline cations, in particular sodium, potassium, lithium, ammonium or primary, secondary or tertiary aliphatic and / or cyclic such as stearylamine, ethanolamines (mono-, di-, triethanolamine), mono and diethylamine, cyclohexylamine, Methylcyclohexylamine, aminomethylpropanol, morpholine, or alternatively for polyvalent function, those selected from the group consisting of alkaline earth divalent cations, in particular magnesium and calcium, or even zinc, as well as trivalent cations, and in particular aluminum, or even some cations of higher valence.
14. The process according to one of claims 1 to 13, characterized in that the comb-like polymer coming from the polymerization reaction can, before or after the total or partial neutralization reaction, be treated and separated into several phases, according to static or dynamic processes, by one or several polar solvents belonging to the group constituted by water, methanol, ethanol, propanol, isopropanol, butanols, acetone, tetrahydrofuran or their mixtures.
15. 15. The process according to one of claims 1 to 14, characterized in that the polymer is dried.
16. 16. Coating sauces, characterized because they are obtained by the process in accordance with one of the claims 1 to 15.
17. 17. Use of the coating sauces according to claim 16, for coating paper and cardboard.