EP0261039B1 - Complex pigmentary compositions for coating paper - Google Patents

Complex pigmentary compositions for coating paper Download PDF

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Publication number
EP0261039B1
EP0261039B1 EP87420222A EP87420222A EP0261039B1 EP 0261039 B1 EP0261039 B1 EP 0261039B1 EP 87420222 A EP87420222 A EP 87420222A EP 87420222 A EP87420222 A EP 87420222A EP 0261039 B1 EP0261039 B1 EP 0261039B1
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Prior art keywords
compositions
agent
pigment
dispersing agent
pigment compositions
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EP87420222A
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German (de)
French (fr)
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EP0261039A1 (en
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Olivier Gonnet
Jean Vallas
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Coatex SAS
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Société COATEX Société Anonyme
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof

Definitions

  • the invention relates to complex pigment compositions for coating paper, containing one or more pigments in high concentration and having a low viscosity which is stable over time.
  • paper pigment compositions comprising pigments, more generally of a given type such as kaolin, containing more or less significant amounts of clays, a phase aqueous in which these pigments are dispersed, at least one binding agent which can be water-dispersed or water-soluble, of natural origin such as starch, casein, carboxymethylcellulose, and / or synthetic such as styrene-butadiene emulsions, styrene- acrylate, vinyl copolymers, and a dispersing agent such as for example a polyphosphate.
  • pigments more generally of a given type such as kaolin, containing more or less significant amounts of clays, a phase aqueous in which these pigments are dispersed
  • at least one binding agent which can be water-dispersed or water-soluble, of natural origin such as starch, casein, carboxymethylcellulose, and / or synthetic such as styrene-butadiene emulsions, styrene-
  • the pigment compositions for coating the paper had to simultaneously contain the smallest amount of water possible to decrease the thermal energy consumed during drying and have the most favorable rheological characteristics for the coating operation, that is to say being in a state of low viscosity at a high speed gradient to allow a much faster coating or alternatively allow at low shear rate to always have a low viscosity in order to be able to easily handle the coating composition, in particular in the sieving operations preceding the operation d coating.
  • Pigment compositions for coating paper have evolved considerably in recent years to meet technological progress (significant increase in speeds) and the imperatives of productivity, quality and costs. This evolution of the coating compositions is manifest, not only by the reduction in the amount of water, that is to say by the increase in the concentration of pigment materials, but also by the use of polyacrylates of alkali metals. or ammonium as dispersing agents. Thus, and by these means, the pigments should be maintained after their mechanical disintegration in a satisfactory dispersed state so that the coating composition is sufficiently fluid.
  • pigment compositions currently available to those skilled in the art for coating paper have also evolved considerably by their pigment formulation, it being understood that they increasingly use mixtures of pigments comprising , no longer kaolin alone or associated with clays, but kaolin and / or pigmentary calcium carbonate and / or talc and / or titanium dioxide, changing the ionic state of the aqueous phase and that, when their preparation and their mixture preceding the coating of the paper and / or their storage, manifests the increase already mentioned in the viscosities and the solidification in certain cases of the said compositions, in particular when there is a mixture of pigments.
  • the Applicant which has previously encountered the phenomenon of increased viscosities during the grinding of mineral materials in an aqueous medium, has already successfully advocated the use of a grinding, ethylenic polymer, making it possible to increase the concentration of mineral matter in the suspension subjected to grinding while maintaining a low viscosity and stable over time, that is to say during grinding and prolonged storage (one month) crushed suspensions.
  • French patent 2,531,444 describes a grinding agent constituted by a polymer and / or copolymer of ethylenic acids, the acid functions of which are partially neutralized by at least one neutralizing agent having at least one monovalent function with a neutralization rate which can vary between 0.40 and 0.96 and preferably between 0.50 and 0.75, the nature of the neutralizing cation not being essential, the important character being the free acidity after neutralization.
  • a pigment composition intended for coating paper comprising at the highest concentration, for example 70%, a single pigment, such as for example kaolin, or several pigments, such as for example pigmentary calcium carbonate and titanium dioxide, there is a very significant increase in viscosity ranging in certain extreme cases until the setting of said composition, while, due to its behavior as a grinding agent, one could expect a decrease in viscosity.
  • French patent 2,539,137 also describes a grinding agent formed from a polymer and / or a copolymer of ethylene acids, the acid functions of which are completely and simultaneously neutralized by at least one neutralizing agent having of a monovalent function and by at least one neutralizing agent having a polyvalent function, the neutralization rate of the agent having a monovalent function being between 0.40 and 0.95, preferably between 0.60 and 0.90 and the neutralization rate of the agent having a polyvalent function being between 0.60 and 0.05, preferably between 0.40 and 0.10.
  • this grinding agent is used according to the practice of the prior art as a dispersing agent in pigment compositions intended for coating paper comprising at a higher concentration a single pigment (kaolin, for example Dinkie A lump at 68% concentration) or a mixture of several pigments (calcium carbonate and titanium dioxide), there is a rapid and irreversible evolution of the rheological characteristics of these compositions, manifested by a strong increase in their viscosity and, in certain case, by their solidification, in particular when there is a mixture of pigment, even when one of them is present in very small proportion.
  • kaolin for example Dinkie A lump at 68% concentration
  • a mixture of several pigments calcium carbonate and titanium dioxide
  • Japanese patent JP- (A) 6,099,334 describes a dispersing agent produced by copolymerization of maleic anhydride and isobutylene, the acid functions of which are completely and simultaneously occupied by the Ca2 + and Na + ions (according to a ratio of 0.7 / 0.3).
  • the dispersant is used in pigment compositions intended for coating paper according to the above conditions, the same phenomenon of deterioration of the rheological characteristics of these compositions occurs. (viscosity not measurable due to solidification).
  • the invention aims to remedy the aforementioned drawbacks by developing complex pigment compositions for coating paper, into which is introduced a dispersing agent giving said compositions a low viscosity and stable over time and excellent compatibility between pigments, avoiding any solidification.
  • a polyvalent salification agent has the capacity to associate with as many carboxylic functions of the polymer as its cation has valences.
  • the dispersing agent is a water-soluble carboxylic polymer of which at least 60% of the carboxylic functions are salified with an appropriate salifying agent having a polyvalent function, it being found that at least 60% of the carboxylic functions salified with said agent and, a fortiori with a monovalent agent, said polymer used as a dispersing agent in complex pigment compositions intended for coating paper causes an increase in their viscosity and their solidification in certain cases.
  • the transfer agents used during the polymerization are those well known to those skilled in the art such as, for example, isopropanol, tertiododecylmercaptan, thioglycolic acid and its esters, n-dodecylmercaptan, 2 mercaptopropionic acid, thiodiethanol.
  • the polymerization medium can be water, methanol, ethanol, propanol, isopropanol, butanols, or alternatively dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, hexane, heptane, benzene, toluene, xylene, acetic, tartaric, lactic, citric, gluconic, glucoheptonic acids, halogenated solvents such as carbon tetrachloride, chloroform, methylene chloride, methyl chloride, ethers of ethylene glycol and propylene glycol.
  • dimethylformamide dimethyl sulfoxide
  • tetrahydrofuran acetone
  • methyl ethyl ketone ethyl acetate
  • butyl acetate hexane
  • the water-soluble carboxylic polymers according to the invention generally have a specific viscosity (measured in the form of the sodium salt) preferably between 0.30 and 1.0.
  • the capillary tube is generally chosen in such a way that the flow time of the NaCl solution, devoid of polymer and / or copolymer, is approximately 90 to 100 seconds, thus giving very specific measurements of specific viscosity. precision.
  • the salifying agent having a polyvalent function is chosen from the group consisting of at least one of the divalent alkaline-earth cations, in particular calcium, magnesium, zinc, copper, lead, as well as by trivalent cations including in particular aluminum, chromium, or even by cations of higher valence.
  • the salification of the dispersing agent according to the invention with at least one salifying agent having a polyvalent function can be carried out at a rate ranging from 0.6 to 1.0.
  • the remaining acid sites can be maintained in this acid state or else completely salified according to the known art by a any salifying agent with a monovalent function, such as alkali cations, in particular lithium, sodium, potassium and by assimilation ammonium or even with an amine.
  • a any salifying agent with a monovalent function such as alkali cations, in particular lithium, sodium, potassium and by assimilation ammonium or even with an amine.
  • the dispersing agent is introduced into the pigment compositions at a concentration of 0.10 to 1.5 and preferably from 0.15 to 1.0 percent by weight relative to the dry pigments.
  • compositions contain pigments, alone or as a mixture, chosen from those known to those skilled in the art, such as for example kaolin, calcium carbonate, talc, titanium dioxide, hydroxide 'aluminum.
  • the pigmentary compositions according to the invention contain at least one binding and / or water-retaining agent chosen from binders of natural or synthetic origin, the former such as for example starch, carboxymethylcellulose, alcohol polyvinyl which also play the role of water retentive, being put in aqueous solution, the others such as for example styrene-butadiene or styrene-acrylate copolymers, being in the form of an aqueous emulsion.
  • the former such as for example starch, carboxymethylcellulose, alcohol polyvinyl which also play the role of water retentive, being put in aqueous solution
  • the others such as for example styrene-butadiene or styrene-acrylate copolymers, being in the form of an aqueous emulsion.
  • the binding agent and / or water expander is introduced into the pigment compositions according to the invention in an amount of 7 to 20 percent by weight relative to the dry pigments.
  • the pigment compositions according to the invention may also contain conventional additives in a known manner, such as anti-foaming agents, optical brighteners, biocidal agents, dyes, alkali hydroxides, etc.
  • the usual additives are introduced into the pigment compositions in the amounts necessary for each case to obtain the properties desired by the formulator, these amounts being well known to those skilled in the art.
  • the pigment compositions according to the invention are prepared according to methods known to those skilled in the art.
  • the pigment compositions according to the invention constitute considerable progress in the field of coating of paper by the facts, not only that they contain a complex pigment formulation (mixture of pigments) and to higher concentration, but still that they have the most favorable rheological characteristics for the coating operation, that is to say being in a state of low viscosity at high speed gradient but also the most favorable for the operations handling such as sieving, transfer by pump, that is to say allowing to always have a low viscosity at low shear rate.
  • pigment compositions for coating paper were prepared according to known methods, making use, for some of the well-known dispersing agents, for the others of dispersing agents which are objects of the invention.
  • tests 1 and 2 In a first group of tests (tests 1 and 2), was determined for a given pH conventionally practiced in the paper industry, the optimum concentration range of dispersing agent according to the invention to be introduced into said compositions for their impart a very low and constant viscosity.
  • Test 1 concerns pigment compositions whose pigment, kaolin Dinkie A lump (English China Clay, Great Britain), is suspended in water at a rate of 71% by weight relative to the total mass in the presence of polyacrylate sodium of specific viscosity 0.4 (salification rate 1), dispersing agent of the prior art introduced into said compositions at increasing rates expressed in percent by weight of dry / dry.
  • Test 2 relates to pigment compositions containing 71% by weight relative to the total mass of kaolin Dinkie A lump suspended in water in the presence of an acrylic polymer of specific viscosity 0.4, salified at a rate of 0 , 7 per Ca2 and at a rate of 0.3 per Na ⁇ , dispersing agent according to the invention introduced into said compositions according to increasing rates expressed in percent by weight of dry / dry.
  • tests 3 and 4 In a second group of tests (tests 3 and 4), a pH range was studied for a given concentration of dispersing agent, this range corresponding to the pH of the components used in the paper industry for the preparation of coating compositions.
  • Test 3 relates to pigment compositions containing 71% by weight relative to the total mass of Dinkie A lump kaolin suspended in water in the presence of the same sodium polyacrylate (salification rate 1) as test 1, agent dispersant of the prior art introduced into said compositions at a constant rate of 0.25% by weight expressed in sec / sec, the pH of said compositions varying between 7.35 and 10.25.
  • Test 4 relates to pigmentary compositions also containing 71% by weight relative to the total mass of kaolin Dinkie A lump suspended in water in the presence of the same calcium and sodium polyacrylate from test 2, dispersing agent according to l he invention introduced into said compositions at a constant rate of 0.25% by weight expressed in sec / sec, the pH of said compositions varying between 7.35 and 10.25.
  • This example relates to the preparation of pigmentary compositions for coating paper making use of dispersing agents which are acrylic polymers of specific viscosities (measured in the form of sodium salt) included in the preferential range of 0.3 to 1, salified at a rate of at least 0.60 by at least one salifying agent having a divalent function.
  • dispersing agents which are acrylic polymers of specific viscosities (measured in the form of sodium salt) included in the preferential range of 0.3 to 1, salified at a rate of at least 0.60 by at least one salifying agent having a divalent function.
  • Test 5 relates to a pigment composition for coating paper comprising 72% by weight of Ti0 2 (titanium dioxide Anatase from THANN AND MULHOUSE) relative to the total mass in the presence of 0.35% by weight (relative to the pigment mass) of dispersing agents (acrylic polymers) which, according to the prior art, are completely salified by the sodium ion.
  • Ti0 2 titanium dioxide Anatase from THANN AND MULHOUSE
  • dispersing agents acrylic polymers
  • Tests 6 to 24 relate to pigment compositions for coating the paper in accordance with the invention, comprising 72% by weight of Ti0 2 (titanium dioxide Anatase from THANN AND MULHOUSE) relative to the total mass in the presence of 0.35% by weight (relative to the dry weight of pigment) of dispersing agents (acrylic polymers) salified at a rate of at least 0.6 by a salifying agent having a divalent function.
  • Ti0 2 titanium dioxide Anatase from THANN AND MULHOUSE
  • This test consists in introducing into a pigment composition based on titanium dioxide a very small amount (1% by weight relative to the mass of Ti0 2 ) of an aqueous suspension of finely ground calcium carbonate (H-90 from OMYA France), said suspension of calcium carbonate having a concentration of 75% by weight relative to its total mass, then to observe after this introduction the evolution of the viscosity of said pigment composition which may lead to solidification.
  • a pigment composition based on titanium dioxide a very small amount (1% by weight relative to the mass of Ti0 2 ) of an aqueous suspension of finely ground calcium carbonate (H-90 from OMYA France), said suspension of calcium carbonate having a concentration of 75% by weight relative to its total mass
  • This example pursues the aim of showing the universal character of the invention by the use in pigmentary compositions of titanium dioxide of various origins.
  • pigmentary compositions for the coating of paper were prepared according to known methods (tests 25 to 27, Ti0 2 AHR of TIOXIDE and tests 28 to 30, Ti0 2 A KRONOS) suspended in water at a rate of 72% by weight relative to the total mass in the presence of a dispersing agent which is either a sodium polyacrylate (specific viscosity 0.4 and salification rate 1) in the case tests relating to the prior art (tests 25, 26, 28, 29), ie an acrylic polymer (specific viscosity 0.4) salified at a rate of 0.7 with Ca2 + and at a rate of 0.3 with Na + in the case of tests relating to the invention (tests 27 and 30).
  • a dispersing agent which is either a sodium polyacrylate (specific viscosity 0.4 and salification rate 1) in the case tests relating to the prior art (tests 25, 26, 28, 29), ie an acrylic polymer (specific viscosity 0.4) salified at a rate of 0.7 with Ca2 + and at a rate of 0.3 with
  • Table IV confirms the conclusions of Table III of Example 2 which are particularly favorable to the subject of the invention.
  • pigmentary compositions for the coating of paper based on kaolin Alphacoat Were prepared according to known methods, using, for some, a dispersing agent belonging to the prior art, for the others a dispersing agent belonging to the invention.
  • Test 31 relates to pigment compositions comprising kaolin Alphacoat in suspension in water at a rate of 68% by weight relative to the total mass and a dispersing agent according to the prior art which is a sodium polyacrylate of specific viscosity 0 , 4 introduced into said compositions according to increasing rates expressed in percent by weight of dry / dry.
  • Test 32 relates to pigment compositions comprising the same kaolin Alphacoat suspended in water at the same concentration and a dispersing agent according to the invention which is an acrylic polymer (specific viscosity 0.4) salified at a rate of 0, 7 with Ca2 +. and a level of 0.3 per Na + introduced into said compositions according to increasing levels.
  • a dispersing agent according to the invention which is an acrylic polymer (specific viscosity 0.4) salified at a rate of 0, 7 with Ca2 +. and a level of 0.3 per Na + introduced into said compositions according to increasing levels.
  • Test 33 relates to pigment compositions comprising the same Alphacoat kaolin suspended in water at the same concentration of 68% and a dispersing agent of the prior art which is the same as that of test 31, introduced into said compositions at a rate of 0.25% by weight expressed in sec / sec, the pH of said compositions varying between 6.7 and 10.25.
  • Test 34 relates to pigment compositions comprising the same Alphacoat kaolin in suspension in water at the same concentration of 68% and a dispersing agent according to the invention which is the same calcium and sodium polyacrylate as in test 32 , introduced into said compositions at a constant rate of 0.25% by weight expressed in sec / sec, the pH of said compositions varying from 6.5 to 10.0.
  • This example which illustrates the invention compared to the prior art, relates to the preparation of pigment compositions for coating paper making use of dispersing agents which are acrylic polymers with a specific viscosity 0.4 (measured in the form of sodium salt).
  • Tests 35 and 37 relate to aqueous pigment compositions for coating paper comprising natural calcium carbonate (from OMYA with a specific surface BET 7 m 2 / g: test 35) or precipitated calcium carbonate (Socal P3 from SOLVAY: test 37, with a BET specific surface area of 14 m 2 / g) in the presence of a dispersing agent (aforementioned acrylic polymer) which, according to the prior art, is completely salified with sodium ion.
  • a dispersing agent aforementioned acrylic polymer
  • Tests 36 and 38 relate to aqueous pigment compositions for coating the paper in accordance with the invention, comprising these same natural calcium carbonates (test 36) or precipitated calcium (test 38) in the presence of a dispersing agent (polymer aforementioned acrylic) which, according to the invention, is salified at a rate of 0.7 with Ca2 + and a rate of 0.3 with Na +.
  • a dispersing agent polymer aforementioned acrylic
  • This example illustrates the implementation according to the invention in an aqueous pigment composition of a dispersing agent which is an acrylic polymer of specific viscosity 0.4, partially salified at the rate of 0.7 with Ca2 +, the other functions -COOH remaining free.
  • a dispersing agent which is an acrylic polymer of specific viscosity 0.4, partially salified at the rate of 0.7 with Ca2 +, the other functions -COOH remaining free.
  • the purpose of this example is to illustrate comparatively complex pigment compositions (mixture of two pigments) for coating paper according to the prior art and according to the invention.
  • compositions in which the dispersing agent is, for some known types (sodium polyacrylate) and for others a salified polymer according to the invention (salification rate: 0.7 Ca2 + and 0.3 Na +).
  • the pH of these coating compositions was adjusted to 8.6 ⁇ 0.1 and the concentration in% by weight of dry matter was 69%.
  • the coating compositions were subjected to Brookfield viscosity measurements at rotational speeds of 10 rpm and 100 rpm with an appropriate mobile.
  • This example illustrates by comparison complex pigment compositions (mixture of three pigments) intended for the coating of paper, prepared according to known methods and making use for some of the dispersing agents belonging to the prior art and for the others of salified dispersing agents according to the invention.
  • the coating compositions thus prepared were subjected to Brookfield viscosity measurements at rotational speeds of 10 rpm and 100 rpm

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Description

L'invention concerne des compositions pigmentaires complexes pour l'enduction du papier, contenant en haute concentration un ou plusieurs pigments et disposant d'une viscosité basse et stable dans le temps.The invention relates to complex pigment compositions for coating paper, containing one or more pigments in high concentration and having a low viscosity which is stable over time.

Depuis longtemps déjà, l'homme de l'art dispose pour l'enduction du papier de compositions pigmentaires comportant des pigments, plus généralement d'un type donné tel que le kaolin, contenant des quantités plus ou moins importantes d'argiles, une phase aqueuse dans laquelle sont dispersés ces pigments, au moins un agent liant qui peut être hydrodispersé ou hydrosoluble, d'origine naturelle tel que l'amidon, la caséine, la carboxyméthylcellulose, et / ou synthétique tel que les émulsions styrène-butadiène, styrène-acrylate, copolymères vinyliques, et un agent dispersant tel que par exemple un polyphosphate.For a long time already, those skilled in the art have had for the coating of paper pigment compositions comprising pigments, more generally of a given type such as kaolin, containing more or less significant amounts of clays, a phase aqueous in which these pigments are dispersed, at least one binding agent which can be water-dispersed or water-soluble, of natural origin such as starch, casein, carboxymethylcellulose, and / or synthetic such as styrene-butadiene emulsions, styrene- acrylate, vinyl copolymers, and a dispersing agent such as for example a polyphosphate.

Or, les techniques d'enduction du papier ayant rapidement évolué parce que les technologies appropriées se sont améliorées et que les vitesses d'enduction ont augmenté, il s'est imposé à l'usager que les compositions pigmentaires pour l'enduction du papier devaient simultanément contenir la plus faible quantité d'eau possible pour diminuer l'énergie thermique consommée lors du séchage et disposer des caractéristiques rhéologiques les plus favorables à l'opération d'enduction, c'est-à-dire être dans un état de faible viscosité à haut gradient de vitesse pour permettre une enduction beaucoup plus rapide ou bien encore permetrre à faible taux de cisaillement d'avoir toujours une viscosité faible pour pouvoir manipuler aisément la composition d'enduction, en particulier dans les opérations de tamisage précédant l'opération d'enduction.However, since the techniques for coating paper have rapidly evolved because the appropriate technologies have improved and the coating speeds have increased, it became obvious to the user that the pigment compositions for coating the paper had to simultaneously contain the smallest amount of water possible to decrease the thermal energy consumed during drying and have the most favorable rheological characteristics for the coating operation, that is to say being in a state of low viscosity at a high speed gradient to allow a much faster coating or alternatively allow at low shear rate to always have a low viscosity in order to be able to easily handle the coating composition, in particular in the sieving operations preceding the operation d coating.

Les compositions pigmentaires pour l'enduction du papier ont beaucoup évolué ces dernières années pour répondre aux progrès technologiques (augmentation importante des vitesses) et aux impératifs de productivité, de qualité et de coûts. Cette évolution des compositions pour enduction est manifeste, non seulement par la réduction de la quantité d'eau, c'est-à-dire par l'augmentation de la concentration en matières pigmentaires, mais encore par l'usage de polyacrylates des métaux alcalins ou d'ammonium comme agents dispersants. Ainsi, et par ces moyens, les pigments devraient être maintenus après leur délitage mécanique dans un état dispersé satisfaisant pour que la composition d'enduction soit suffisamment fluide.Pigment compositions for coating paper have evolved considerably in recent years to meet technological progress (significant increase in speeds) and the imperatives of productivity, quality and costs. This evolution of the coating compositions is manifest, not only by the reduction in the amount of water, that is to say by the increase in the concentration of pigment materials, but also by the use of polyacrylates of alkali metals. or ammonium as dispersing agents. Thus, and by these means, the pigments should be maintained after their mechanical disintegration in a satisfactory dispersed state so that the coating composition is sufficiently fluid.

A ce titre, le brevet français 2 185 721 décrit des compositions pigmentaires pour l'enduction du papier dont l'agent dispersant est choisi parmi les polymères d'acide acrylique complètement neutralisés par une solution alcaline d'hydroxyde de sodium. Or, de tels agents dispersants présentent des inconvénients qui sont considérés comme majeurs car ils se sont révélés difficiles d'emploi dans certaines compositions pigmentaires actuellement utilisées dans l'enduction du papier, tant ils se sont montrés sensibles aux variations du pH de la phase aqueuse de la dispersion pigmentaire de l'environnement ionique desdites compositions, cette sensibilité étant décelée par l'augmentation rapide et irréversible de la viscosité et, dans certains cas, une prise en masse des compositions d'enduction.As such, French patent 2,185,721 describes pigment compositions for coating paper, the dispersing agent of which is chosen from acrylic acid polymers completely neutralized by an alkaline solution of sodium hydroxide. However, such dispersing agents have drawbacks which are considered to be major because they have proved difficult to use in certain pigment compositions currently used in the coating of paper, as they have been shown to be sensitive to variations in the pH of the aqueous phase. of the pigmentary dispersion of the ionic environment of said compositions, this sensitivity being detected by the rapid and irreversible increase in viscosity and, in certain cases, solidification of the coating compositions.

Car les compositions pigmentaires mises actuellement à la disposition de l'homme de l'art pour l'enduction du papier ont également beaucoup évolué par leur formulation pigmentaire, étant entendu qu'elles mettent de plus en plus souvent en oeuvre des mélanges de pigments comportant, non plus du kaolin seul ou associé à des argiles, mais du kaolin et/ou du carbonate de calcium pigmentaire et/ou du talc et/ou du dioxyde de titane, changeant l'état ionique de la phase aqueuse et que, lors de leur préparation et de leur mélange précédant l'enduction du papier et/ou de leur stockage, se manifeste l'augmentation déjà évoquée des viscosités et la prise en masse dans certains cas desdites compositions, en particulier quand il y a mélange de pigments.Because the pigment compositions currently available to those skilled in the art for coating paper have also evolved considerably by their pigment formulation, it being understood that they increasingly use mixtures of pigments comprising , no longer kaolin alone or associated with clays, but kaolin and / or pigmentary calcium carbonate and / or talc and / or titanium dioxide, changing the ionic state of the aqueous phase and that, when their preparation and their mixture preceding the coating of the paper and / or their storage, manifests the increase already mentioned in the viscosities and the solidification in certain cases of the said compositions, in particular when there is a mixture of pigments.

Ainsi, ces agents dispersants se sont dévoilés à l'usage incapables de résoudre ou de surmonter les inconvénients provoqués au sein des compositions pour l'enduction du papier par la présence de mélanges de pigments plus ou moins compatibles entre eux, mais dont cette présence est nécessaire dans lesdites compositions pour la qualité du papier après couchage.Thus, these dispersing agents have been revealed in use incapable of solving or overcoming the drawbacks caused within compositions for coating paper by the presence of mixtures of pigments which are more or less compatible with each other, but whose presence is necessary in said compositions for the quality of the paper after coating.

Toutefois, dans un autre domain, la Demanderesse, qui s'est antérieurement heurtée au phénomène d'augmentation des viscosités lors du broyage de matières minérales en un milieu aqueux, a déjà préconisé avec succès dans ce domaine l'usage d'un agent de broyage, polymère éthylénique, permettant d'augmenter la concentration en matière minérale dans la suspension soumise au broyage tout en maintenant une viscosité basse et stable dans le temps, c'est-à-dire pendant le broyage et le stockage prolongé (un mois) des suspensions broyées.However, in another field, the Applicant, which has previously encountered the phenomenon of increased viscosities during the grinding of mineral materials in an aqueous medium, has already successfully advocated the use of a grinding, ethylenic polymer, making it possible to increase the concentration of mineral matter in the suspension subjected to grinding while maintaining a low viscosity and stable over time, that is to say during grinding and prolonged storage (one month) crushed suspensions.

A cet égard, le brevet français 2 531 444 décrit un agent de broyage constitué par un polymère et/ou copolymère d'acides éthyléniques dont les fonctions acides sont partiellement neutralisés par au moins un agent de neutralisation disposant d'au moins une fonction monovalente avec un taux de neutralisation pouvant varier entre 0,40 et 0,96 et préférentiellement entre 0,50 et 0,75, la nature du cation neutralisant n'étant pas essentielle, le caractère important étant l'acidité libre après neutralisation.In this regard, French patent 2,531,444 describes a grinding agent constituted by a polymer and / or copolymer of ethylenic acids, the acid functions of which are partially neutralized by at least one neutralizing agent having at least one monovalent function with a neutralization rate which can vary between 0.40 and 0.96 and preferably between 0.50 and 0.75, the nature of the neutralizing cation not being essential, the important character being the free acidity after neutralization.

Or, quand ledit agent de broyage, comme le préconise l'art antérieur, est introduit dans une composition pigmentaire destinée à l'enduction du papier comportant à la plus haute concentration, par exemple 70%, un seul pigment, tel que par exemple le kaolin, ou plusieurs pigments, tels que par exemple du carbonate de calcium pigmentaire et du dioxyde de titane, il se produit une augmentation très importante de la viscosité allant dans certains cas extrêmes jusqu'à la prise en masse de ladite composition, alors que, en raison de son comportement en tant qu'agent de broyage, on pouvait attendre une baisse de la viscosité.However, when said grinding agent, as recommended by the prior art, is introduced into a pigment composition intended for coating paper comprising at the highest concentration, for example 70%, a single pigment, such as for example kaolin, or several pigments, such as for example pigmentary calcium carbonate and titanium dioxide, there is a very significant increase in viscosity ranging in certain extreme cases until the setting of said composition, while, due to its behavior as a grinding agent, one could expect a decrease in viscosity.

A ce même égard, le brevet français 2 539 137 décrit aussi un agent de broyage formé d'un polymère et/ou d'un copolymère d'acides ethylèniques dont les fonctions acides sont complètement et simultanément neutralisées par au moins un agent de neutralisation disposant d'une fonction monovalente et par au moins un agent de neutralisation disposant d'une fonction polyvalente, le taux de neutralisation de l'agent disposant d'une fonction monovalente étant compris entre 0,40 et 0,95, préférentiellement entre 0,60 et 0,90 et le taux de neutralisation de l'agent disposant d'une fonction polyvalente étant compris entre 0,60 et 0,05, préférentiellement entre 0,40 et 0,10.In this same respect, French patent 2,539,137 also describes a grinding agent formed from a polymer and / or a copolymer of ethylene acids, the acid functions of which are completely and simultaneously neutralized by at least one neutralizing agent having of a monovalent function and by at least one neutralizing agent having a polyvalent function, the neutralization rate of the agent having a monovalent function being between 0.40 and 0.95, preferably between 0.60 and 0.90 and the neutralization rate of the agent having a polyvalent function being between 0.60 and 0.05, preferably between 0.40 and 0.10.

Or, quand cet agent de broyage est mis en oeuvre selon la pratique de l'art antérieur comme agent dispersant dans des compositions pigmentaires destinées à l'enduction du papier comportant à une plus haute concentration un seul pigment (kaolin, par exemple Dinkie A lump à 68% de concentration) ou un mélange de plusieurs pigments (carbonate de calcium et dioxyde de titane), il se produit une évolution rapide et irréversible des caractéristiques rhéologiques de ces compositions, se manifestant par une forte augmentation de leur viscosité et, dans certains cas, par leur prise en masse, en particulier quand il y a mélange de pigment, même quand l'une d'entre eux est présent en très faible proportion.However, when this grinding agent is used according to the practice of the prior art as a dispersing agent in pigment compositions intended for coating paper comprising at a higher concentration a single pigment (kaolin, for example Dinkie A lump at 68% concentration) or a mixture of several pigments (calcium carbonate and titanium dioxide), there is a rapid and irreversible evolution of the rheological characteristics of these compositions, manifested by a strong increase in their viscosity and, in certain case, by their solidification, in particular when there is a mixture of pigment, even when one of them is present in very small proportion.

"Dans ce même esprit, le brevet japonais JP-(A) 6 099 334 décrit un agent dispersant réalisé par copolymérisation d'anhydride maléique et d'isobutylène dont les fonctions acides sont complètement et simultanément occupées par les ions Ca2+ et Na+ (selon un ratio 0,7/0,3). Mais, dès lors que le dispersant est mis en oeuvre dans des compositions pigmentaires destinées à l'enduction du papier selon les conditions précitées se produit le même phénomène de détérioration des caractéristiques rhéologiques de ces compositions (viscosité non mesurable à cause d'une prise en masse).""In this same spirit, Japanese patent JP- (A) 6,099,334 describes a dispersing agent produced by copolymerization of maleic anhydride and isobutylene, the acid functions of which are completely and simultaneously occupied by the Ca2 + and Na + ions (according to a ratio of 0.7 / 0.3). However, as soon as the dispersant is used in pigment compositions intended for coating paper according to the above conditions, the same phenomenon of deterioration of the rheological characteristics of these compositions occurs. (viscosity not measurable due to solidification). "

Dès lors, l'invention a pour but de remédier aux inconvénients précités par la mise au point de compositions pigmentaires complexes pour l'enduction du papier, dans lesquelles est introduit un agent dispersant conférant aux dites compositions une viscosité basse et stable dans le temps et une excellente compatibilité entre pigments, évitant toute prise en masse.Therefore, the invention aims to remedy the aforementioned drawbacks by developing complex pigment compositions for coating paper, into which is introduced a dispersing agent giving said compositions a low viscosity and stable over time and excellent compatibility between pigments, avoiding any solidification.

Selon l'invention, les compositions pigmentaires complexes pour l'enduction du papier, comprenant une phase aqueuse, au moins un pigment d'origine minérale, un agent liant, divers additifs usuels bien connus et un agent dispersant constitué par des polymères carboxyliques hydrosolubles sous une forme salifiée, obtenues par les procédés connus de polymérisation, se caractérisent en ce que l'agent dispersant

  • a) dispose d'une viscosité spécifique comprise entre 0,25 et 2 (mesurée sous la forme de sel de sodium),
  • b) est salifié à un taux d'au moins 0,60 par au moins un agent de salification disposant d'une fonction polyvalente.
According to the invention, complex pigment compositions for coating paper, comprising an aqueous phase, at least one pigment of mineral origin, a binding agent, various usual well-known additives and a dispersing agent consisting of water-soluble carboxylic polymers under a salified form, obtained by known polymerization processes, are characterized in that the dispersing agent
  • a) has a specific viscosity of between 0.25 and 2 (measured in the form of the sodium salt),
  • b) is salified at a rate of at least 0.60 by at least one salifying agent having a versatile function.

Pour permettre la meilleure compréhension de l'objet de l'invention, il est souhaitable de rappeler qu'un agent de salification polyvalent possède la capacité de s'associer à autant de fonctions carboxyliques du polymère que son cation possède de valences.To allow a better understanding of the subject of the invention, it is desirable to recall that a polyvalent salification agent has the capacity to associate with as many carboxylic functions of the polymer as its cation has valences.

Parce que la Demanderesse a été conduite à poursuivre ses recherches dans le domaine des agents dispersants destinés aux compositions pigmentaires pour l'enduction du papier et, par là même, à multiplier les essais industriels, elle a été amenée à observer d'abord puis à vérifier ensuite qu'il était possible de réaliser des compositions pigmentaires pour l'enduction du papier plus concentrées en matières sèches que celles réalisées selon l'art antérieur, de formulation pigmentaire complex mettant en oeuvre des mélanges de pigments et de viscosité faible et très stable dans le temps exempte de toute prise en masse. Ces conditions sont obtenues quant l'agent dispersant est un polymère carboxylique hydrosoluble dont 60% au moins des fonctions carboxyliques sont salifiées par un agent salifiant approprié disposant d'une fonction polyvalente, étant constaté qu'à moins de 60% des fonctions carboxyliques salifiées avec ledit agent et, a fortiori avec un agent monovalent, ledit polymère mis en oeuvre comme agent dispersant dans des compositions pigmentaires complexes destinées à l'enduction du papier provoque une augmentation de leur viscosité et leur prise en masse dans certains cas.Because the Applicant was led to continue its research in the field of dispersing agents intended for pigment compositions for the coating of paper and, thereby, to increase industrial tests, it was led to observe first and then to then check that it was possible to produce pigmentary compositions for coating paper more concentrated in dry materials than those produced according to the prior art, of complex pigmentary formulation using mixtures of pigments and of low and very stable viscosity in time free from any solidification. These conditions are obtained when the dispersing agent is a water-soluble carboxylic polymer of which at least 60% of the carboxylic functions are salified with an appropriate salifying agent having a polyvalent function, it being found that at least 60% of the carboxylic functions salified with said agent and, a fortiori with a monovalent agent, said polymer used as a dispersing agent in complex pigment compositions intended for coating paper causes an increase in their viscosity and their solidification in certain cases.

Les polymères carboxyliques constituant l'agent dispersant selon l'invention résultent de la polymèri- sation en présence d'agents de transfert selon les procédés connus en milieu aqueux, alcoolique, hy- droalcoolique, aromatique ou aliphatique de l'un au moins des monomères suivants :

  • acide acrylique, méthacrylique, itàconique, crotonique, fumarique, anhydride maléique ou encore isocrotonique, aconitique, mésaconique, sinapique, undécylénique, angélique, hydroxy-acrylique, l'acroléine, l'acrylamide, l'acrylonitrile, les esters des acides acryliques et méthacryliques et, en particulier, les acrylates et méthacrylates de méthyle, éthyle, propyle, le méthacrylate de diméthylaminoéthyle, les imidazoles, vinylpyrolidone, vinylcaprolactame, l'éthylène, le propylène, l'isobutylène, le diisobutylène, l'acétate de vinyle, le styrène, l'alphaméthylstyrène, la méthylvinylcétone.
The carboxylic polymers constituting the dispersing agent according to the invention result from the polymerization in the presence of transfer agents according to known methods in aqueous, alcoholic, hydroalcoholic, aromatic or aliphatic medium of at least one of the monomers following:
  • acrylic, methacrylic, itonic, crotonic, fumaric, maleic anhydride or isocrotonic, aconitic, mesaconic, sinapic, undecylenic, angelic, hydroxy-acrylic, acrolein, acrylamide, acrylonitrile, esters of acrylic and methacrylic acids and, in particular, methyl, ethyl and propyl acrylates and methacrylates, dimethylaminoethyl methacrylate, imidazoles, vinylpyrolidone, vinylcaprolactam, ethylene, propylene, isobutylene, diisobutylene, vinyl acetate, styrene , alphamethylstyrene, methylvinyl ketone.

Les agents de transfert mis en oeuvre au cours de la polymérisation sont ceux bien connus de l'homme de l'art tels que par exmple l'isopropanol, le tertiododécylmercaptan, l'acide thioglycolique et ses esters, le n-dodécylmercaptan, l'acide de 2 mercaptopropionique, le thiodiéthanol.The transfer agents used during the polymerization are those well known to those skilled in the art such as, for example, isopropanol, tertiododecylmercaptan, thioglycolic acid and its esters, n-dodecylmercaptan, 2 mercaptopropionic acid, thiodiethanol.

Ainsi, le milieu de poly mérisation peut être l'eau, le méthanol, l'éthanol, le propanol, l'isopropanol, les butanols, ou encore le diméthylformamide, le diméthylsulfoxyde, le tétrahydrofurane, l'acétone, la méthyl- éthylcétone, l'acétate d'éthyle, l'acétate de butyle, l'hexane, l'heptane, le benzène, le toluène, le xylène, les acides acétiques, tartrique, lactique, citrique, gluconique, glucoheptonique, les solvants halogénés comme le tétrachlorure de carbone, le chloroforme, le chlorure de méthylène, le chlorure de méthyle, les éthers de l'éthylèneglycol et du propylèneglycol.Thus, the polymerization medium can be water, methanol, ethanol, propanol, isopropanol, butanols, or alternatively dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, hexane, heptane, benzene, toluene, xylene, acetic, tartaric, lactic, citric, gluconic, glucoheptonic acids, halogenated solvents such as carbon tetrachloride, chloroform, methylene chloride, methyl chloride, ethers of ethylene glycol and propylene glycol.

Les polymères carboxyliques hydrosolubles selon l'invention ont généralement une viscosité spécifique (mesurée sous la forme du sel de sodium) préférentiellement comprise entre 0,30 et 1,0.The water-soluble carboxylic polymers according to the invention generally have a specific viscosity (measured in the form of the sodium salt) preferably between 0.30 and 1.0.

La viscosité spécifique des polymères et/ou copolymères carboxyliques, qui est symbolisée par la lettre "n", est déterminée de la manière suivante :

  • on prépare une solution de polymère et/ou copolymère carboxylique neutralisé à 100% (taux de neutralisation : 1 ) par l'hydroxyde de sodium pour la mesure, par dissolution de 50 g sec du polymère et/ou copolymère dans un litre d'une solution d'eau distillée contenant 60 g de NaCI. Puis on mesure avec un viscosimètre capillaire de constante de Baume égale à 0,000105 placé dans un bain thermostaté à 25° C, le temps d'écoulement d'un volume donné de la solution précitée contenant le polymère et/ou copolymère carboxylique alcalin, ainsi que le temps d'écoulement du même volume de solution aqueuse de Chlorure de Sodium dépourvue dudit polymère et/ou copolymère. Il est alors possible de définir la viscosité "11" grâce à la relation suivante :
    Figure imgb0001
The specific viscosity of the carboxylic polymers and / or copolymers, which is symbolized by the letter "n", is determined as follows:
  • a solution of 100% neutralized carboxylic polymer and / or copolymer is prepared (neutralization rate: 1) with sodium hydroxide for the measurement, by dissolving 50 g dry of the polymer and / or copolymer in one liter of a distilled water solution containing 60 g of NaCl. Then a capillary viscometer with a Baume constant equal to 0.000105 placed in a bath thermostatically controlled at 25 ° C. is measured the flow time of a given volume of the above-mentioned solution containing the alkaline carboxylic polymer and / or copolymer, as well as the flow time of the same volume of aqueous sodium chloride solution devoid of said polymer and / or copolymer. It is then possible to define the viscosity " 11 " thanks to the following relation:
    Figure imgb0001

Le tube capillaire est généralement choisi de telle manière que le temps d'écoulement de la solution de NaCI, dépourvue de polymère et/ou copolymère, soit d'environ 90 à 100 secondes, donnant ainsi des mesures de viscosité spécifique d'une très bonne précision.The capillary tube is generally chosen in such a way that the flow time of the NaCl solution, devoid of polymer and / or copolymer, is approximately 90 to 100 seconds, thus giving very specific measurements of specific viscosity. precision.

L'agent salifiant disposant d'une fonction polyvalente est choisi dans le groupe constitué par l'un au moins des cations divalents alcalino-terreux, en particulier le calcium, le magnésium, le zinc, le cuivre, le plomb, ainsi que par les cations trivalents dont en particulier l'aluminium, le chrome, ou encore par des cations de valence supérieure.The salifying agent having a polyvalent function is chosen from the group consisting of at least one of the divalent alkaline-earth cations, in particular calcium, magnesium, zinc, copper, lead, as well as by trivalent cations including in particular aluminum, chromium, or even by cations of higher valence.

La salification de l'agent dispersant selon l'invention par au moins un agent de salification disposant d'une fonction polyvalente peut être réalisée à un taux compris dans l'intervalle de 0,6 à 1.0.The salification of the dispersing agent according to the invention with at least one salifying agent having a polyvalent function can be carried out at a rate ranging from 0.6 to 1.0.

Dès que la salification d'au moins 60% des sites acides par au moins un agent salifiant disposant d'une fonction polyvalente est effectuée, les sites acides restants peuvent être maintenus dans cet état acide ou bien salifiés complètement selon l'art connu par un quelconque agent salifiant à fonction monovalente, tels que les cations alcalins, en particulier le lithium, le sodium, le potassium et par assimilation l'ammonium ou encore par une amine.As soon as the salification of at least 60% of the acid sites with at least one salifying agent having a polyvalent function is carried out, the remaining acid sites can be maintained in this acid state or else completely salified according to the known art by a any salifying agent with a monovalent function, such as alkali cations, in particular lithium, sodium, potassium and by assimilation ammonium or even with an amine.

L'agent dispersant est introduit dans les compositions pigmentaires à une concentration de 0,10 à 1,5 et préférentiellement de 0,15 à 1,0 pour cent en poids par rapport aux pigments secs.The dispersing agent is introduced into the pigment compositions at a concentration of 0.10 to 1.5 and preferably from 0.15 to 1.0 percent by weight relative to the dry pigments.

Outre l'agent dispersant selon l'invention, lesdites compositions contiennent des pigments, seuls ou en mélange, choisis parmi ceux connus de l'homme de métier, tels que par exemple kaolin, carbonate de calcium, talc, dioxyde de titane, hydroxyde d'aluminium.In addition to the dispersing agent according to the invention, said compositions contain pigments, alone or as a mixture, chosen from those known to those skilled in the art, such as for example kaolin, calcium carbonate, talc, titanium dioxide, hydroxide 'aluminum.

De plus, les compositions pigmentaries selon l'invention contiennent au moins un agent liant et/ou rétenteur d'eau choisi parmi les liants d'origine naturelle ou synthétique, les premiers tels que par exemple l'amidon, la carboxyméthylcellulose, l'alcool polyvinylique qui jouent également le rôle de rétenteur d'eau, étant mis en solution aqueuse, les autres tels que par exemple les copolymères styrène-butadiène ou styrène-acrylate, se présentant sous la forme d'une émulsion aqueuse.In addition, the pigmentary compositions according to the invention contain at least one binding and / or water-retaining agent chosen from binders of natural or synthetic origin, the former such as for example starch, carboxymethylcellulose, alcohol polyvinyl which also play the role of water retentive, being put in aqueous solution, the others such as for example styrene-butadiene or styrene-acrylate copolymers, being in the form of an aqueous emulsion.

L'agent liant et/ou r étenteur d'eau est introduit dans les compositions pigmentaires selon l'invention à raison de 7 à 20 pour cent en poids par rapport aux pigments secs.The binding agent and / or water expander is introduced into the pigment compositions according to the invention in an amount of 7 to 20 percent by weight relative to the dry pigments.

De même, les compositions pigmentaires selon l'invention peuvent également contenir de manière connue des additifs usuels, tels que des agents anti-mousse, des azurants optiques, des agents biocides, des colorants, des hydroxydes alcalins...Likewise, the pigment compositions according to the invention may also contain conventional additives in a known manner, such as anti-foaming agents, optical brighteners, biocidal agents, dyes, alkali hydroxides, etc.

Les additifs usuels sont introduits dans les compositions pigmentaires selon les quantités nécessaires à chaque cas d'espèce pour obtenir les propriétés désirées par le formulateur, ces quantités étant bien connues de l'homme de l'art.The usual additives are introduced into the pigment compositions in the amounts necessary for each case to obtain the properties desired by the formulator, these amounts being well known to those skilled in the art.

En pratique, les compositions pigmentaires selon l'invention peuvent contenir, exprimées en pour cent en poids par rapport à la masse pigmentaire minérale anhydre :

  • a) de 0,10 à 1,5 et préférentiellement de 0,15 à 1,0 pour cent de l'agent dispersant,
  • b) de 7 à 20 pour cent de l'agent liant et/ou rétenteur d'eau,
  • c) éventuellement des additifs usuels selon les pour cent connus.
In practice, the pigment compositions according to the invention may contain, expressed in percent by weight relative to the anhydrous mineral pigment mass:
  • a) from 0.10 to 1.5 and preferably from 0.15 to 1.0 percent of the dispersing agent,
  • b) from 7 to 20 percent of the binding agent and / or water-retaining agent,
  • c) optionally usual additives according to the known percent.

Les compositions pigmentaires selon l'invention sont préparées selon les procédés connus de l'homme de l'art.The pigment compositions according to the invention are prepared according to methods known to those skilled in the art.

Ainsi et contrairement à l'art antérieur, les compositions pigmentaires selon l'invention constituent un progrès considérable dans le domaine de l'enduction du papier par les faits, non seulement qu'elles contiennent une formulation pigmentaire complexe (mélange de pigments) et à concentration plus élevée, mais encore qu'elles disposent des caractéristiques rhéologiques les plus favorables à l'opération d'enduction, c'est-à-dire être dans un état de faible viscosité à haut gradient de vitesse mais aussi les plus favorables aux opérations de manipulation telles que tamisage, transfert par pompe, c'est-à-dire permettre d'avoir toujours une faible viscosité à faible taux de cisaillement.Thus, and unlike the prior art, the pigment compositions according to the invention constitute considerable progress in the field of coating of paper by the facts, not only that they contain a complex pigment formulation (mixture of pigments) and to higher concentration, but still that they have the most favorable rheological characteristics for the coating operation, that is to say being in a state of low viscosity at high speed gradient but also the most favorable for the operations handling such as sieving, transfer by pump, that is to say allowing to always have a low viscosity at low shear rate.

L'invention sera mieux comprise grâce à l'illustration qui en est faite à travers les exemples suivants.The invention will be better understood thanks to the illustration which is made thereof through the following examples.

Exemple 1Example 1

Cet exemple poursuit le but d'illustrer comparativement l'art antérieur et l'invention.This example pursues the aim of illustrating comparatively the prior art and the invention.

Pour ce faire, on a préparé selon les procédés connus des compositions pigmentaires pour l'enduction du papier en faisant usage, pour les unes d'agents dispersants bien connus, pour les autres d'agents dispersants objets de l'invention.To do this, pigment compositions for coating paper were prepared according to known methods, making use, for some of the well-known dispersing agents, for the others of dispersing agents which are objects of the invention.

Dans un premier groupe d'essais (essais 1 et 2), a été déterminé pour un pH donné classiquement pratiqué dans l'industrie papetière, l'intervalle de concentration optimale d'agent dispersant selon l'invention à introduire dans lesdites compositions pour leur conférer une viscosité très faible et constante.In a first group of tests (tests 1 and 2), was determined for a given pH conventionally practiced in the paper industry, the optimum concentration range of dispersing agent according to the invention to be introduced into said compositions for their impart a very low and constant viscosity.

L'essai 1 concerne des compositions pigmentaires dont le pigment, kaolin Dinkie A lump (English China Clay, Grande Bretagne), est mis en suspension dans l'eau à raison de 71 % en poids par rapport à la masse totale en présence de polyacrylate de sodium de viscosité spécifique 0,4 (taux de salification 1), agent dispersant de l'art antérieur introduit dans lesdites compositions à des taux croissants exprimés en pour cent en poids de sec/sec.Test 1 concerns pigment compositions whose pigment, kaolin Dinkie A lump (English China Clay, Great Britain), is suspended in water at a rate of 71% by weight relative to the total mass in the presence of polyacrylate sodium of specific viscosity 0.4 (salification rate 1), dispersing agent of the prior art introduced into said compositions at increasing rates expressed in percent by weight of dry / dry.

L'essai 2 concerne des compositions pigmentaires contentant 71% en poids par rapport à la masse totale de kaolin Dinkie A lump en suspension dans l'eau en présence d'un polymère acrylique de viscosité spécifique 0,4, salifié à un taux de 0,7 par Ca2 et à un taux de 0,3 par Na±, agent dispersant selon l'invention introduit dans lesdites compositions selon des taux croissants exprimés en pour cent en poids de sec/sec.Test 2 relates to pigment compositions containing 71% by weight relative to the total mass of kaolin Dinkie A lump suspended in water in the presence of an acrylic polymer of specific viscosity 0.4, salified at a rate of 0 , 7 per Ca2 and at a rate of 0.3 per Na ±, dispersing agent according to the invention introduced into said compositions according to increasing rates expressed in percent by weight of dry / dry.

Le pH de ces compositions était réglé sur 7,4 ± 0,1.The pH of these compositions was adjusted to 7.4 ± 0.1.

Toutes ces compositions pigmentaires ont été soumises à des mesures de viscosités Brookfield à des vitesses de rotation de 10 tours et 100 tours par minute avec un mobile approprié selon les viscosités, ces viscosités étant mesurées à la fin de la préparation.All these pigment compositions were subjected to Brookfield viscosity measurements at rotational speeds of 10 revolutions and 100 revolutions per minute with an appropriate mobile according to the viscosities, these viscosities being measured at the end of the preparation.

Tous les résultats concernant les compositions précitées ont été consignés dans le tableau 1 ci-après et sont illustrés par la figure 1.

Figure imgb0002

  • A.A = Art Antérieur
  • INV = Invention
All the results relating to the abovementioned compositions have been recorded in Table 1 below and are illustrated by FIG. 1.
Figure imgb0002
  • AA = Prior Art
  • INV = Invention

Le tableau montre qu'à concentrations égales en agents dispersants :

  • - la viscosité des compositions pigmentaires est toujours plus faible pour celles faisant l'objet de l'invention,
  • - la viscosité des compositions pigmentaires selon l'invention reste constante à partir d'un seuil de 0,22% jusqu'à 0,25% en poids de sec/sec en agent dispersant, intervalle le plus favorable pour l'utilisateur, alors que celle des compositions de l'art antérieur augmente lorsque l'on augmente la quantité d'agent dispersant.
The table shows that at equal concentrations of dispersing agents:
  • the viscosity of the pigment compositions is always lower for those forming the subject of the invention,
  • the viscosity of the pigment compositions according to the invention remains constant from a threshold of 0.22% up to 0.25% by weight of dry / dry in dispersing agent, the most favorable interval for the user, then that that of the compositions of the prior art increases when the quantity of dispersing agent is increased.

Dans un deuxième groupe d'essais (essais 3 et 4) a été étudié un intervalle de pH pour une concentration donnée en agent dispersant cet intervalle correspondant aux pH des composants utilisés dans l'industrie papetière pour la préparation des compositions d'enduction.In a second group of tests (tests 3 and 4), a pH range was studied for a given concentration of dispersing agent, this range corresponding to the pH of the components used in the paper industry for the preparation of coating compositions.

Car, il est connu que dans des compositions d'enduction appartenant à l'art antérieur, l'homme de métier règle le pH des compositions de kaolin à environ 7,3 valeur pour laquelle la viscosité est la plus faible et que l'ajustement des pH des divers composants entrant dans les dites compositions d'enduction évite des chocs dus à ces différences de pH que se matérialiseraient par une augmentation indésirable de la viscosité.Because, it is known that in coating compositions belonging to the prior art, a person skilled in the art adjusts the pH of the kaolin compositions to around 7.3 value for which the viscosity is the lowest and that the adjustment the pH of the various components used in said coating compositions avoids shocks due to these differences in pH which would materialize by an undesirable increase in viscosity.

L'essai 3 concerne des compositions pigmentaires contentant 71% en poids par rapport à la masse totale de kaolin Dinkie A lump en suspension dans l'eau en présence du même polyacrylate de sodium (taux de salification 1) que l'essai 1, agent dispersant de l'art antérieur introduit dans lesdites compositions à un taux constant de 0,25% en poids exprimé en sec/sec, le pH desdites compositions évoluant entre 7,35 et 10,25.Test 3 relates to pigment compositions containing 71% by weight relative to the total mass of Dinkie A lump kaolin suspended in water in the presence of the same sodium polyacrylate (salification rate 1) as test 1, agent dispersant of the prior art introduced into said compositions at a constant rate of 0.25% by weight expressed in sec / sec, the pH of said compositions varying between 7.35 and 10.25.

L'essai 4 concerne des compositions pigmentaires contenant également 71% en poids par rapport à la masse totale de kaolin Dinkie A lump en suspension dans l'eau en présence du même polyacrylate de calcium et sodium de l'essai 2, agent dispersant selon l'invention introduit dans lesdites compositions à un taux constant de 0,25% en poids exprimé en sec/sec, le pH desdites compositions évoluant entre 7,35 et 10,25.Test 4 relates to pigmentary compositions also containing 71% by weight relative to the total mass of kaolin Dinkie A lump suspended in water in the presence of the same calcium and sodium polyacrylate from test 2, dispersing agent according to l he invention introduced into said compositions at a constant rate of 0.25% by weight expressed in sec / sec, the pH of said compositions varying between 7.35 and 10.25.

Ces compositions pigmentaires ont été soumises aux mêmes mesures de viscosité Brookfield que celles pratiquées pour les essais 1 et 2.These pigment compositions were subjected to the same Brookfield viscosity measurements as those carried out for tests 1 and 2.

Tous les résultats concernant ces compositions ont été consignés dans le tableau Il ci-après et sont illustrés par la figure 2.

Figure imgb0003
All the results concerning these compositions have been recorded in Table II below and are illustrated by FIG. 2.
Figure imgb0003

Le tableau Il révèle qu'en faisant évoluer le pH des compositions pigmentaires précitées pour une même concentration en agent dispersant :

  • - la viscosité des compositions selon l'invention est toujours inférieure à celle des compositions selon l'art antérieur quelle que soit la valeur du pH,
  • - la viscosité des compositions selon l'invention est stable quel que soit le pH alors que celle des compositions selon l'art antérieur augmente avec le pH.
Table II reveals that by changing the pH of the above-mentioned pigment compositions for the same concentration of dispersing agent:
  • the viscosity of the compositions according to the invention is always lower than that of the compositions according to the prior art regardless of the pH value,
  • - The viscosity of the compositions according to the invention is stable whatever the pH while that of the compositions according to the prior art increases with the pH.

Exemple 2Example 2

Cet exemple, dont le but est d'illustrer l'invention, concerne la préparation de compositions pigmentaires pour l'enduction du papier faisant usage d'agents dispersants qui sont des polymères acryliques de viscosités spécifiques (mesurées sous la forme de sel de sodium) comprises dans l'intervalle préférentiel de 0,3 à 1, salifiés à un taux d'au moins 0,60 par au moins un agent de salification disposant d'une fonction divalente.This example, the aim of which is to illustrate the invention, relates to the preparation of pigmentary compositions for coating paper making use of dispersing agents which are acrylic polymers of specific viscosities (measured in the form of sodium salt) included in the preferential range of 0.3 to 1, salified at a rate of at least 0.60 by at least one salifying agent having a divalent function.

L'essai 5 concerne une composition pigmentaire pour l'enduction du papier comprenant 72% en poids de Ti02 (dioxyde de titane Anatase de THANN ET MULHOUSE) par rapport à la masse totale en présence de 0,35% en poids ( par rapport à la masse de pigment) d'agents dispersants (polymères acryliques) qui, selon l'art antérieur, sont complètement salifiés par l'ion sodium.Test 5 relates to a pigment composition for coating paper comprising 72% by weight of Ti0 2 (titanium dioxide Anatase from THANN AND MULHOUSE) relative to the total mass in the presence of 0.35% by weight (relative to the pigment mass) of dispersing agents (acrylic polymers) which, according to the prior art, are completely salified by the sodium ion.

Les essais 6 à 24 ont trait à des compositions pigmentaires pour l'enduction du papier conformes à l'invention, comprenant 72% en poids de Ti02 (dioxyde de titane Anatase de THANN ET MULHOUSE) par rapport à la masse totale en présence de 0,35% en poids ( par rapport au poids sec de pigment), d'agents dispersants (polymères acryliques) salifiés à un taux d'au moins 0,6 par un agent de salification ayant une fonction divalente.Tests 6 to 24 relate to pigment compositions for coating the paper in accordance with the invention, comprising 72% by weight of Ti0 2 (titanium dioxide Anatase from THANN AND MULHOUSE) relative to the total mass in the presence of 0.35% by weight (relative to the dry weight of pigment) of dispersing agents (acrylic polymers) salified at a rate of at least 0.6 by a salifying agent having a divalent function.

Toutes les compositions pigmentaires ont été soumises à des mesures de viscosités à des vitesses de rotation de 10 tours et 100 tours par minute (viscosimètre Brookfield) avec un mobile approprié selon les viscosités, ces viscosités étant mesurées à la fin de la préparation.All the pigment compositions were subjected to viscosity measurements at rotational speeds of 10 revolutions and 100 revolutions per minute (Brookfield viscometer) with an appropriate mobile according to the viscosities, these viscosities being measured at the end of the preparation.

De plus, pour mettre en évidence les effets néfastes se produisant dans les installations industrielles, en particulier dans les tuyauteries, pompes, cuves de stockage lors des passages successifs dans ces installations de compositions pigmentaires différentes, par exemple l'une à base de carbonate de calcium, l'autre à base de dioxyde de titane, on a réalisé en laboratoire un test de compatibilité entre ces deux compositions.In addition, to highlight the harmful effects occurring in industrial installations, in particular in pipes, pumps, storage tanks during successive passages in these installations of different pigment compositions, for example one based on carbonate of calcium, the other based on titanium dioxide, a compatibility test between these two compositions was carried out in the laboratory.

Ce test consiste à introduire dans une composition pigmentaire à base de dioxyde de titane une très faible quantité (1 % en poids par rapport à la masse de Ti02) d'une suspension aqueuse de carbonate de calcium finement broyé ( H-90 de OMYA France),ladite suspension de carbonate de calcium ayant une concentration de 75% en poids par rapport à sa masse totale, puis à observer après cette introduction l'évolution de la viscosité de ladite composition pigmentaire pouvant aboutir à une prise en masse.This test consists in introducing into a pigment composition based on titanium dioxide a very small amount (1% by weight relative to the mass of Ti0 2 ) of an aqueous suspension of finely ground calcium carbonate (H-90 from OMYA France), said suspension of calcium carbonate having a concentration of 75% by weight relative to its total mass, then to observe after this introduction the evolution of the viscosity of said pigment composition which may lead to solidification.

Tous les paramètres et résultats concernant les compositions précitées ont été consignés dans le tableau III ci-après.

Figure imgb0004
All the parameters and results relating to the abovementioned compositions have been recorded in Table III below.
Figure imgb0004

Le tableau III montre par comparaison de l'essai 5 avec les essais 6 à 24 :

  • - l'importante diminution des viscosités des compositions pigmentaires qui deviennent mesurables quand on passe de l'art antérieur à l'objet de l'invention. On peut mettre en oeuvre les pigments à cette concentration par opposition à l'art antérieur,
  • - l'influence très bénéfique de la salification des agents dispersants à un taux d'au moins 0,6 par au moins un agent de salification polyvalent,
  • - la bonne compatibilité entre pigments (dioxyde de titane anatase et carbonate de calcium) pour les compositions pigmentaires selon l'invention.
Table III shows by comparison of test 5 with tests 6 to 24:
  • - The significant decrease in the viscosities of the pigment compositions which become measurable when moving from the prior art to the subject of the invention. The pigments can be used at this concentration as opposed to the prior art,
  • - the very beneficial influence of the salification of dispersing agents at a rate of at least 0.6 by at least one polyvalent salification agent,
  • - the good compatibility between pigments (titanium dioxide anatase and calcium carbonate) for the pigment compositions according to the invention.

Exemple 3Example 3

Cet exemple poursuit le but de montrer le caractère universel de l'invention par la mise en oeuvre dans les compositions pigmentaires de dioxyde de titane de diverses origines.This example pursues the aim of showing the universal character of the invention by the use in pigmentary compositions of titanium dioxide of various origins.

Pour ce faire, on a préparé selon les procédés connus des compositions pigmentaires pour l'enduction du papier dont le pigment est du dioxyde de titane (essais 25 à 27, Ti02 AHR de TIOXIDE et essais 28 à 30, Ti02 A KRONOS) mis en suspension dans l'eau à raison de 72% en poids par rapport à la masse totale en présence d'un agent dispersant qui est, soit un polyacrylate de sodium (viscosité spécifique 0,4 et taux de salification 1) dans le cas des essais relatifs à l'art antérieur (essais 25, 26, 28, 29), soit un polymère acrylique (viscosité spécifique 0,4) salifié à un taux de 0,7 par Ca2+ et à un taux de 0,3 par Na+ dans le cas des essais concernant l'invention (essais 27 et 30).To do this, pigmentary compositions for the coating of paper, the pigment of which is titanium dioxide, were prepared according to known methods (tests 25 to 27, Ti0 2 AHR of TIOXIDE and tests 28 to 30, Ti0 2 A KRONOS) suspended in water at a rate of 72% by weight relative to the total mass in the presence of a dispersing agent which is either a sodium polyacrylate (specific viscosity 0.4 and salification rate 1) in the case tests relating to the prior art (tests 25, 26, 28, 29), ie an acrylic polymer (specific viscosity 0.4) salified at a rate of 0.7 with Ca2 + and at a rate of 0.3 with Na + in the case of tests relating to the invention (tests 27 and 30).

Toutes les compositions pigmentaires ont été soumises aux mêmes mesures de viscosité et aux mêmes tests de compatibilité que ceux pratiqués dans l'exemple 2.All the pigment compositions were subjected to the same viscosity measurements and to the same compatibility tests as those practiced in Example 2.

Tous les résultats relatifs aux compositions précitées ont été introduits dans le tableau IV ci-après.

Figure imgb0005
All the results relating to the abovementioned compositions have been introduced in Table IV below.
Figure imgb0005

Le tableau IV confirme les conclusions du tableau III de l'exemple 2 particulièrement favorables à l'objet de l'invention.Table IV confirms the conclusions of Table III of Example 2 which are particularly favorable to the subject of the invention.

Exemple 4Example 4

Cet exemple permet d'illustrer le caractère universel de l'invention par la mise en oeuvre dans les compositions pigmentaires de kaolin en tant que pigments d'une origine autre que celui mis en oeuvre dans l'exemple 1.This example illustrates the universal nature of the invention by the use in kaolin pigment compositions as pigments of an origin other than that used in Example 1.

Dans ce but, on a préparé selon les procédés connus des compositions pigmentaires pour l'enduction du papier à base de kaolin Alphacoat (ANGLO AMERICAN CLAYS CORP.) mettant en oeuvre, pour les unes un agent dispersant appartenant à l'art antérieur, pour les autres un agent dispersant appartenant à l'invention.For this purpose, pigmentary compositions for the coating of paper based on kaolin Alphacoat (ANGLO AMERICAN CLAYS CORP.) Were prepared according to known methods, using, for some, a dispersing agent belonging to the prior art, for the others a dispersing agent belonging to the invention.

L'essai 31 concerne des compositions pigmentaires comprenant du kaolin Alphacoat en suspension dans l'eau à raison de 68% en poids par rapport à la masse totale et un agent dispersant selon l'art antérieur qui est un polyacrylate de sodium de viscosité spécifique 0,4 introduit dans lesdites compositions selon des taux croissants exprimés en pour cent en poids de sec/sec.Test 31 relates to pigment compositions comprising kaolin Alphacoat in suspension in water at a rate of 68% by weight relative to the total mass and a dispersing agent according to the prior art which is a sodium polyacrylate of specific viscosity 0 , 4 introduced into said compositions according to increasing rates expressed in percent by weight of dry / dry.

L'essai 32 concerne des compositions pigmentaires comprenant le même kaolin Alphacoat en suspension dans l'eau à la même concentration et un agent dispersant selon l'invention qui est un polymère acrylique (viscosité spécifique 0,4) salifié à un taux de 0,7 par du Ca2+. et un taux de 0,3 par du Na+ introduit dans lesdites compositions selon des taux croissants.Test 32 relates to pigment compositions comprising the same kaolin Alphacoat suspended in water at the same concentration and a dispersing agent according to the invention which is an acrylic polymer (specific viscosity 0.4) salified at a rate of 0, 7 with Ca2 +. and a level of 0.3 per Na + introduced into said compositions according to increasing levels.

Le pH de ces compositions était réglé sur 7,1 ± 0,1.The pH of these compositions was adjusted to 7.1 ± 0.1.

Toutes ces compositions pigmentaires ont été soumises aux mesures de viscosités Brookfield et les résultats les concernant ont été réunis dans le tableau V ci-après et sont illustrés par la figure 3.

Figure imgb0006
Ce tableau confirme les conclusions extraites du tableau I qui concernait un kaolin Dinkie A lump.All these pigment compositions were subjected to Brookfield viscosity measurements and the results relating to them were collated in Table V below and are illustrated by FIG. 3.
Figure imgb0006
 This table confirms the conclusions extracted from Table I which concerned a Dinkie A lump kaolin.

L'essai 33 concerne des compositions pigmentaires comprenant le même kaolin Alphacoat en suspension dans l'eau à la même concentration de 68% et un agent dispersant de l'art antérieur qui est le même que celui de l'essai 31, introduit dans lesdites compositions à un taux de 0,25% en poids exprimé en sec/sec, le pH desdites compositions évoluant entre 6,7 et 10,25.Test 33 relates to pigment compositions comprising the same Alphacoat kaolin suspended in water at the same concentration of 68% and a dispersing agent of the prior art which is the same as that of test 31, introduced into said compositions at a rate of 0.25% by weight expressed in sec / sec, the pH of said compositions varying between 6.7 and 10.25.

L'essai 34 concerne des compositions pigmentaires comprenant le même kaolin Alphacoat en suspension dans l'eau à la même concentration de 68% et un agent dispersant selon l'invention qui est le même polyacrylate de calcium et de sodium que dans l'essai 32, introduit dans lesdites compositions à un taux constant de 0,25% en poids exprimé en sec/sec, le pH desdites compositions évoluant de 6,5 à 10,0.Test 34 relates to pigment compositions comprising the same Alphacoat kaolin in suspension in water at the same concentration of 68% and a dispersing agent according to the invention which is the same calcium and sodium polyacrylate as in test 32 , introduced into said compositions at a constant rate of 0.25% by weight expressed in sec / sec, the pH of said compositions varying from 6.5 to 10.0.

Les résultats relatifs à ces compositions pigmentaires ont été réunis dans le tableau VI ci-après et sont illustrés par la figure 4.

Figure imgb0007
Ce tableau apporte les mêmes conclusions que le tableau Il concernant un kaolin Dinkie A lump.The results relating to these pigment compositions have been collated in Table VI below and are illustrated in FIG. 4.
Figure imgb0007
 This table brings the same conclusions as table II concerning a kaolin Dinkie A lump.

Exemple 5Example 5

Cet exemple, qui illustre l'invention comparativement à l'art antérieur, concerne la préparation de compositions pigmentaires pour l'enduction du papier faisant usage d'agents dispersants qui sont des polymères acryliques de viscosité spécifique 0,4 (mesurée sous la forme de sel de sodium).This example, which illustrates the invention compared to the prior art, relates to the preparation of pigment compositions for coating paper making use of dispersing agents which are acrylic polymers with a specific viscosity 0.4 (measured in the form of sodium salt).

Les essais 35 et 37 concernent des compositions aqueuses pigmentaires pour l'enduction du papier comprenant du carbonate de calcium naturel (de OMYA de surface spécifique BET 7 m2/g : essai 35) ou du carbonate de calcium précipité (Socal P3 de SOLVAY : essai 37, de surface spécifique BET 14 m2/g) en présence d'un agent dispersant (polymère acrylique précité) qui, selon l'art antérieur, est complètement salifié par l'ion sodium.Tests 35 and 37 relate to aqueous pigment compositions for coating paper comprising natural calcium carbonate (from OMYA with a specific surface BET 7 m 2 / g: test 35) or precipitated calcium carbonate (Socal P3 from SOLVAY: test 37, with a BET specific surface area of 14 m 2 / g) in the presence of a dispersing agent (aforementioned acrylic polymer) which, according to the prior art, is completely salified with sodium ion.

Les essais 36 et 38 ont trait à des compositions aqueuses pigmentaires pour l'enduction du papier conformes à l'invention, comprenant ces mêmes carbonates de calcium naturel (essai 36) ou précipité (essai 38) en présence d'un agent dispersant (polymère acrylique précité) qui, selon l'invention, est salifié à un taux de 0,7 par Ca2+ et un taux de 0,3 par Na+. Tests 36 and 38 relate to aqueous pigment compositions for coating the paper in accordance with the invention, comprising these same natural calcium carbonates (test 36) or precipitated calcium (test 38) in the presence of a dispersing agent (polymer aforementioned acrylic) which, according to the invention, is salified at a rate of 0.7 with Ca2 + and a rate of 0.3 with Na +.

Les résultats relatifs à ces compositions sont réunis dans le tableau VII ci-après.

Figure imgb0008
La comparaison des essais 35 et 37 (art antérieur) avec les essais 36 et 38 (invention) confirme bien les importantes améliorations obtenues grâce à l'invention, en particulier quand la surface spécifique BET de pigments augmente de manière conséquente, provoquant dans ce cas des difficultés bien connues de mise en oeuvre.The results relating to these compositions are collated in Table VII below.
Figure imgb0008
 The comparison of tests 35 and 37 (prior art) with tests 36 and 38 (invention) confirms the significant improvements obtained thanks to the invention, in particular when the BET specific surface area of pigments increases significantly, causing in this case well known difficulties of implementation.

Exemple 6Example 6

Cet exemple illustre la mise en oeuvre selon l'invention dans une composition aqueuse pigmentaire d'un agent dispersant qui est un polymère acrylique de viscosité spécifique 0,4, partiellement salifié au taux de 0,7 par du Ca2+, les autres fonctions -COOH restant libres.This example illustrates the implementation according to the invention in an aqueous pigment composition of a dispersing agent which is an acrylic polymer of specific viscosity 0.4, partially salified at the rate of 0.7 with Ca2 +, the other functions -COOH remaining free.

A cet égard, l'essai 39 concerne la préparation d'une composition aqueuse pigmentaire compound 72% en poids par rapport à la masse totale de Ti02 (dioxyde de titane Anatase de THANN ET MULHOUSE) en présence de 0,35% en poids par rapport au poids sec du pigment d'un agent dispersant (polymère acrylique) précité (Ca2+/-COOH = 0,7/0,3).In this regard, test 39 relates to the preparation of an aqueous pigment composition composed of 72% by weight relative to the total mass of Ti0 2 (titanium dioxide Anatase from THANN AND MULHOUSE) in the presence of 0.35% by weight relative to the dry weight of the pigment of a dispersing agent (acrylic polymer) mentioned above (Ca2 +/- COOH = 0.7 / 0.3).

Les résultats relatifs à cette composition ainsi qu'à la composition témoin (essai 5 de l'art antérieur) sont réunis dans le tableau VIII ci-après.

Figure imgb0009
Ainsi, à condition que l'agent dispersant (polymère acrylique) soit salifié à un taux d'au moins 0,6 par un agent de salification ayant une fonction polyvalente, les fonctions acides (-COOH) libres n'affectent en aucun cas les effets très positifs constatés pour les compositions pigmentaires selon l'invention.The results relating to this composition as well as to the control composition (test 5 of the prior art) are collated in Table VIII below.
Figure imgb0009
 Thus, provided that the dispersing agent (acrylic polymer) is salified at a rate of at least 0.6 by a salifying agent having a polyvalent function, the free acid functions (-COOH) in no way affect the very positive effects observed for the pigment compositions according to the invention.

Exemple 7Example 7

Cet exemple a pour but d'illustrer comparativement des compositions pigmentaires complexes (mélange de deux pigments) pour l'enduction du papier selon l'art antérieur et selon l'invention.The purpose of this example is to illustrate comparatively complex pigment compositions (mixture of two pigments) for coating paper according to the prior art and according to the invention.

Pour ce faire on a réalisé selon des procédés connus de préparation des compositions pigmentaires complexes dans lesquelles l'agent dispersant est pour les uns de type connu (polyacrylate de sodium) et pour les autres un polymère salifié selon l'invention (taux de salification : 0,7 Ca2+ et 0,3 Na+).To do this, complex pigmentary compositions in which the dispersing agent is, for some known types (sodium polyacrylate) and for others a salified polymer according to the invention (salification rate: 0.7 Ca2 + and 0.3 Na +).

L'essai 40 concerne une composition pigmentaire complexe selon l'art antérieur contenant :

  • - 70 % en poids de kaolin Dinkie A lump, introduit sous la forme d'une suspension aqueuse dudit kaolin à 71 % en poids de concentration contenant en tant qu'agent dispersant 0,25% en poids sec/sec d'un polyacrylate de sodium de viscosité spécifique 0,4 (taux de salification 1).
  • - 30% en poids de carbonate de calcium pigmentaire introduit sous la forme d'une suspension aqueuse dudit carbonate de calcium à concentration de 74,3% en poids contenant 0,6% en poids sec/sec d'un agent dispersant qui est un polymère acrylique de viscosité spécifique 0,56, salifié à un taux de 0,3 par l'ion Ca2+ et à un taux de 0,7 par l'ion Na+, conforme à l'art antérieur.
Test 40 relates to a complex pigment composition according to the prior art containing:
  • - 70% by weight of Dinkie A lump kaolin, introduced in the form of an aqueous suspension of said kaolin at 71% by weight of concentration containing, as dispersing agent, 0.25% by dry / dry weight of a polyacrylate of sodium with specific viscosity 0.4 (salification rate 1).
  • - 30% by weight of pigmentary calcium carbonate introduced in the form of an aqueous suspension of said calcium carbonate at a concentration of 74.3% by weight containing 0.6% by dry / dry weight of a dispersing agent which is a acrylic polymer of specific viscosity 0.56, salified at a rate of 0.3 with the Ca2 + ion and at a rate of 0.7 with the Na + ion, in accordance with the prior art.

L'essai 41 concerne une composition pigmentaire complexe selon l'invention, contenant :

  • - 70% en poids de kaolin Dinkie A lump, introduit sous la forme d'une suspension aqueuse dudit kaolin à 71% en poids de concentration contenant comme agent dispersant 0,25% en poids sec/sec d'un polymère acrylique de viscosité spécifique 0,40 salifié à un taux de 0,7 par l'ion Ca2+ et à un taux de 0,3 par l'ion Na+
  • - 30% en poids de carbonate de calcium pigmentaire, introduit sous la forme d'une suspension aqueuse décrite dans l'essai 40.
Test 41 relates to a complex pigment composition according to the invention, containing:
  • - 70% by weight of Dinkie A lump kaolin, introduced in the form of an aqueous suspension of said kaolin at 71% by weight of concentration containing as dispersing agent 0.25% by dry / dry weight of an acrylic polymer of specific viscosity 0.40 salified at a rate of 0.7 with the Ca2 + ion and at a rate of 0.3 with the Na + ion
  • - 30% by weight of pigmentary calcium carbonate, introduced in the form of an aqueous suspension described in test 40.

Au terme de ces deux mélanges pigmentaires, on a préparé des compositions pour l'enduction du papier en ajoutant aux essai 40 (art antérieur) et 41 (invention) pour 100 parties en poids de pigments secs :

  • - 0,5 partie en poids d'un rétenteur d'eau (carboxyméthylcellulose)
  • - 10,5 parties en poids d'un latex, émulsion aqueuse anionique d'un copolymère acrylique commercialisé sous l'appellation ACRONAL S 360 D par B.A.S.F.
At the end of these two pigment mixes, compositions for coating the paper were prepared by adding to tests 40 (prior art) and 41 (invention) per 100 parts by weight of dry pigments:
  • - 0.5 part by weight of a water-retaining agent (carboxymethylcellulose)
  • - 10.5 parts by weight of a latex, an anionic aqueous emulsion of an acrylic copolymer sold under the name ACRONAL S 360 D by BASF

Le pH de ces compositions pour enduction était réglé sur 8,6 ± 0,1 et la concentration en % en poids de matières sèches était de 69%.The pH of these coating compositions was adjusted to 8.6 ± 0.1 and the concentration in% by weight of dry matter was 69%.

Les compositions pour enduction ont été soumises à des mesures de viscosité Brookfield à des vitesses de rotation de 10 T/mn et 100 T/mn avec un mobile approprié.The coating compositions were subjected to Brookfield viscosity measurements at rotational speeds of 10 rpm and 100 rpm with an appropriate mobile.

Tous les résultats relatifs à ces compositions ont été consignés dans le tableau IX ci-après.

Figure imgb0010
Le tableau par comparaison des deux compositions pour enduction du papier confirme qu'à concentrations égales en pigments et en agents dispersants, les viscosités de la composition pour enduction du papier selon l'invention sont toujours beaucoup plus faibles (environ 60%) que la composition pour enduction selon l'art antérieur.All the results relating to these compositions are recorded in Table IX below.
Figure imgb0010
 The table by comparison of the two compositions for coating the paper confirms that at equal concentrations of pigments and dispersing agents, the viscosities of the composition for coating the paper according to the invention are always much lower (approximately 60%) than the composition for coating according to the prior art.

Exempte 8Free 8

Cet exemple illustre par comparaison des compositions pigmentaires complexes (mélange de trois pigments) destinées à l'enduction du papier, préparées selon des procédés connus et faisant usage pour les unes d'agents dispersants appartenant à l'art antérieur et pour les autres d'agents dispersants salifiés selon l'invention.This example illustrates by comparison complex pigment compositions (mixture of three pigments) intended for the coating of paper, prepared according to known methods and making use for some of the dispersing agents belonging to the prior art and for the others of salified dispersing agents according to the invention.

L'essai 42 concerne une composition complexe selon l'art antérieur préparée par l'introduction :

  • a) d'abord de 10% en poids de dioxyde de titane (Anatase ATI de la société THANN ET MULHOUSE) sous la forme d'une suspension aqueuse à 72% en poids de concentration contenant également comme agent dispersant 0,1% en poids sec/sec d'un polyacrylate de sodium de viscosité spécifique 0,4 (taux de salification 1)
  • b) ensuite de 20% en poids de carbonate de calcium pigmentaire sous la forme de la suspension aqueuse décrite dans l'essai 40, l'agent dispersant appartenant à l'art antérieur.
  • c) enfin de 70% en poids de kaolin sous la forme de la suspension aqueuse décrite dans l'essai 40, l'agent dispersant appartenant à l'art antérieur.
Test 42 relates to a complex composition according to the prior art prepared by the introduction:
  • a) first of 10% by weight of titanium dioxide (Anatase ATI from the company THANN ET MULHOUSE) in the form of an aqueous suspension at 72% by weight of concentration also containing as dispersing agent 0.1% by weight dry / dry sodium polyacrylate with specific viscosity 0.4 (salification level 1)
  • b) then 20% by weight of pigmentary calcium carbonate in the form of the aqueous suspension described in test 40, the dispersing agent belonging to the prior art.
  • c) finally 70% by weight of kaolin in the form of the aqueous suspension described in test 40, the dispersing agent belonging to the prior art.

L'essai 43 concerne une composition complexe selon l'invention préparée par l'introduction :

  • a) d'abord de 10% en poids de dioxyde de titane (Anatase ATI de la société THANN ET MULHOUSE) sous la forme d'une suspension aqueuse à 72% en poids de concentration contenant également comme agent dispersant, selon l'invention, 0,35% en poids sec/sec d'un polymère acrylique de viscosité spécifique (mesurée sous la forme de sel de sodium) 0,4 et salifié à un taux de 0,7 par l'ion Ca2± et à un taux de 0,3 par l'ion Na±.
  • b) ensuite de 20% en poids de carbonate de calcium pigmentaire sous la forme de la même suspension aqueuse que celle de l'essai 42, paragraphe (b).
  • c) enfin de 70% en poids de kaolin sous la forme de la même suspension aqueuse que celle de l'essai 42, paragraphe (c).
Test 43 relates to a complex composition according to the invention prepared by the introduction:
  • a) first of 10% by weight of titanium dioxide (Anatase ATI from the company THANN ET MULHOUSE) in the form of an aqueous suspension at 72% by weight of concentration also containing as dispersing agent, according to the invention, 0.35% by dry / dry weight of an acrylic polymer of specific viscosity (measured in the form of sodium salt) 0.4 and salified at a rate of 0.7 with the ion Ca2 ± and at a rate of 0.3 per Na ± ion.
  • b) then 20% by weight of pigmentary calcium carbonate in the form of the same aqueous suspension as that of test 42, paragraph (b).
  • c) finally 70% by weight of kaolin in the form of the same aqueous suspension as that of test 42, paragraph (c).

L'essai 44 concerne une composition complexe selon l'invention préparée par l'introduction :

  • a) d'abord de 10% en poids de dioxyde de titane (Anatase ATI de la société THANN ET MULHOUSE) sous la forme d'une suspension aqueuse à 72% en poids de concentration contenant également comme agent dispersant 0,35% en poids sec/sec d'un polymère acrylique de viscosité spécifique (mesurée sous la forme du sel de sodium) 0,4 et salifié à un taux de 0,7 par l'ion Ca2+ et à un taux de 0,3 par l'ion Na+.
  • b) ensuite de 20% en poids de carbonate de calcium pigmentaire sous la forme de la suspension aqueuse décrite dans l'essai 40, l'agent dispersant appartenant à fart antérieur.
  • c) enfin de 70% en poids de kaolin sous la forme d'une suspension aqueuse à une concentration de 71 % en poids contenant comme agent dispersant 0,25% en poids sec/sec d'un polymère acrylique de viscosité spécifique 0,4 salifié à un taux de 0,7 par l'ion Ca2+ et à un taux de 0,3 par l'ion Na+.
Test 44 relates to a complex composition according to the invention prepared by the introduction:
  • a) first of 10% by weight of titanium dioxide (Anatase ATI from the company THANN ET MULHOUSE) in the form of an aqueous suspension at 72% by weight of concentration also containing as dispersing agent 0.35% by weight dry / dry of an acrylic polymer of specific viscosity (measured in the form of the sodium salt) 0.4 and salified at a rate of 0.7 with the Ca2 + ion and at a rate of 0.3 with the ion Na +.
  • b) then 20% by weight of pigmentary calcium carbonate in the form of the aqueous suspension described in test 40, the dispersing agent belonging to the prior art.
  • c) finally 70% by weight of kaolin in the form of an aqueous suspension at a concentration of 71% by weight containing as dispersing agent 0.25% by dry / dry weight of an acrylic polymer of specific viscosity 0.4 salified at a rate of 0.7 with the Ca2 + ion and at a rate of 0.3 with the Na + ion .

L'essai 45 concerne une composition complexe selon l'art antérieur préparée par l'introduction :

  • a) d'abord de 70% en poids de kaolin sous la forme de la suspension aqueuse décrite dans l'essai 40, l'agent dispersant appartenant à l'art antérieur.
  • b) ensuite de 20% en poids de carbonate de calcium pigmentaire sous la forme de la suspension aqueuse décrite dans l'essai 40, l'agent dispersant appartenant à l'art antérieur.
  • c) enfin de 10% en poids de dioxyde de titane (Anatase Atl de la société THANN ET MULHOUSE) sous la forme d'une suspension aqueuse à 72% en poids de concentration contenant également comme agent dispersant 0,1% en poids sec/sec d'un polyacrylate de sodium de viscosité spécifique 0,4 (taux de salification 1 )
Test 45 relates to a complex composition according to the prior art prepared by the introduction:
  • a) first of 70% by weight of kaolin in the form of the aqueous suspension described in test 40, the dispersing agent belonging to the prior art.
  • b) then 20% by weight of pigmentary calcium carbonate in the form of the aqueous suspension described in test 40, the dispersing agent belonging to the prior art.
  • c) finally 10% by weight of titanium dioxide (Anatase Atl from the company THANN ET MULHOUSE) in the form of an aqueous suspension at 72% by weight of concentration also containing as dispersing agent 0.1% by dry weight / dry sodium polyacrylate with specific viscosity 0.4 (salification rate 1)

L'essai 46 concerne une composition complexe selon l'invention préparée par l'introduction :

  • a) d'abord de 70% en poids de kaolin sous la forme de la suspension aqueuse décrite dans l'essai 40, l'agent dispersant appartenant à l'art antérieur.
  • b) ensuite de 20% en poids de carbonate de calcium pigmentaire sous la forme de la suspension aqueuse décrite dans l'essai 40, l'agent dispersant appartenant à l'art antérieur.
  • c) enfin de 10% en poids de dioxyde de titane (Anatase ATI de la société THANN ET MULHOUSE) sous la forme d'une suspension aqueuse à 72% en poids de concentration contenant comme agent dispersant, selon l'invention, 0,35% en poids sec/sec d'un polymère acrylique de viscosité spécifique 0,4 salifié au taux de 0,7 par l'ion Ca2+ et au taux de 0,3 par l'ion Na+.
Test 46 relates to a complex composition according to the invention prepared by the introduction:
  • a) first of 70% by weight of kaolin in the form of the aqueous suspension described in test 40, the dispersing agent belonging to the prior art.
  • b) then 20% by weight of pigmentary calcium carbonate in the form of the aqueous suspension described in test 40, the dispersing agent belonging to the prior art.
  • c) finally 10% by weight of titanium dioxide (Anatase ATI from the company THANN ET MULHOUSE) in the form of an aqueous suspension at 72% by weight of concentration containing, as dispersing agent, according to the invention, 0.35 % by dry / dry weight of an acrylic polymer of specific viscosity 0.4 salified at the rate of 0.7 with the Ca2 + ion and at the rate of 0.3 with the Na + ion.

L'essai 47 concerne une composition complexe selon l'invention préparée par l'introduction :

  • a) d'abord de 70% en poids de kaolin sous la forme de la suspension aqueuse à une concentration de 71 % en poids contenant comme agent dispersant 0,25% en poids sec/sec d'un polymère acrylique de viscosité spécifique 0,4 salifié à un taux de 0,7 par l'ion Ca2+ et à un taux de 0,3 par l'ion Na+.
  • b) ensuite de 20% en poids de carbonate de calcium pigmentaire sous la forme de la suspension aqueuse décrite dans l'essai 40, l'agent dispersant appartenant à l'art antérieur.
  • c) enfin de 10% en poids de dioxyde de titane (Anatase ATI de la société THANN ET MULHOUSE) sous la forme d'une suspension aqueuse à une concentration de 72% en poids contenant également comme agent dispersant, selon l'invention, 0,35% en poids sec/sec d'un polymère acrylique de viscosité spécifique 0,4 salifié à un taux de 0,7 par l'ion Ca2+ et un taux de 0,3 par l'ion Na+.
Test 47 relates to a complex composition according to the invention prepared by the introduction:
  • a) first of 70% by weight of kaolin in the form of the aqueous suspension at a concentration of 71% by weight containing as dispersing agent 0.25% by dry / dry weight of an acrylic polymer of specific viscosity 0, 4 salified at a rate of 0.7 with the Ca2 + ion and at a rate of 0.3 with the Na + ion.
  • b) then 20% by weight of pigmentary calcium carbonate in the form of the aqueous suspension described in test 40, the dispersing agent belonging to the prior art.
  • c) finally 10% by weight of titanium dioxide (Anatase ATI from the company THANN ET MULHOUSE) in the form of an aqueous suspension at a concentration of 72% by weight also containing as dispersing agent, according to the invention, 0 , 35% by dry / dry weight of an acrylic polymer of specific viscosity 0.4 salified at a rate of 0.7 with the Ca2 + ion and a rate of 0.3 with the Na + ion.

Après avoir réalisé ces divers mélanges, pigmentaires, des compositions pour l'enduction du papier ont été préparés en ajoutant aux essais 42 à 47, pour 100 parties en poids de pigments secs :

  • - 0,5 partie en poids d'un rétenteur d'eau (carboxyméthylcellulose),
  • - 10,5 parties en poids, du latex décrit dans l'exemple 7.
After having made these various pigmentary mixtures, compositions for coating the paper were prepared by adding to tests 42 to 47, per 100 parts by weight of dry pigments:
  • - 0.5 part by weight of a water retentant (carboxymethylcellulose),
  • - 10.5 parts by weight, of the latex described in Example 7.

Le pH de ces compositions était réglé à 8,6 ± 0,1 et la concentration en matières sèches à 68,7% ± 0,2%.The pH of these compositions was adjusted to 8.6 ± 0.1 and the dry matter concentration to 68.7% ± 0.2%.

Les compositions pour enduction ainsi préparées ont été soumises à des mesures de viscosité Brookfield à des vitesses de rotation de 10 T/mn et 100 T/mnThe coating compositions thus prepared were subjected to Brookfield viscosity measurements at rotational speeds of 10 rpm and 100 rpm

Tous les résultats relatifs à ces compositions ont été rassemblés dans le tableau X ci-après.

Figure imgb0011
De ce tableau et par comparaison entre les essais concernant l'art antérieur et ceux concernant l'invention, il apparaît que :

  • - dans l'art antérieur, l'ordre d'introduction des suspensions aqueuses pigmentaires lors de la préparation des compositions complexes pour enduction du papier, est important car il a pour conséquence soit une prise en masse (essai 42) soit des viscosités très élevées (essai 45) desdites compositions, révélant une incompatibilité entres les divers pigments
  • - dans l'invention, les suspensions aqueuses pigmentaires réalisées en présence d'au moins un agent dispersant selon l'invention deviennent compatibles entre elles lors de leur mélange grâce à la présence dudit agent. De tels mélanges ne prennent plus en masse quel que soit l'ordre d'introduction des suspensions pigmentaires, et confèrent aux dites compositions complexes ainsi préparées des viscosités beaucoup plus faibles que dans l'art antérieur.
All the results relating to these compositions have been collated in Table X below.
Figure imgb0011
 From this table and by comparison between the tests relating to the prior art and those relating to the invention, it appears that:
  • in the prior art, the order of introduction of the aqueous pigmentary suspensions during the preparation of the complex compositions for coating the paper is important because it results either in solidification (test 42) or in very high viscosities (test 45) of said compositions, revealing an incompatibility between the various pigments
  • - In the invention, the aqueous pigment suspensions produced in the presence of at least one dispersing agent according to the invention become compatible with one another during their mixing thanks to the presence of said agent. Such mixtures no longer solidify regardless of the order of introduction of the pigment suspensions, and give said complex compositions thus prepared viscosities much lower than in the prior art.

Claims (13)

1. Complex pigment compositions for paper coating comprising an aqueous phase, at least one pigment of mineral origin, a binder and a dispersing agent consisting of water-soluble carboxylic polymers in salt form obtained by known polymerisation processes, characterised in that the dispersing agent:
a) has a specific viscosity of between 0.25 and 2 (measured in the form of sodium salt),
b) is converted into a salt to a level of at least 0.60 by a multivalent salt-forming agent.
2. Pigment compositions for paper coating according to claim 1, characterised in that the dispersing agent is the result of the polymerisation or copolymerisation by known processes of at least one of the monomers belonging to the group of acrylic, methacrylic, itaconic, crotonic or fumaric acids, maleic anhydride or isocrotonic, aconitic, mesaconic, sinapic, undecylenic, angelic, hydroxyacrylic acids, acrolein, acrylamide, acrylonitrile, esters of acrylic and methacrylic acids, and in particular methyl, ethyl and propyl acrylates and methacrylates, dimethylaminoethyl methacrylates, imidazoles, vinylpyrrolidone, vinylcaprolactam, vinyl acetate, styrene, alphamethylstyrene, methylvinyl ketone.
3. Pigment compositions for paper coating according to claim 2, characterised in that the dispersing agent is the result of the polymerisation or copolymerisation by known processes of preferentially at least one of the monomers acrylic, methacrylic, itaconic, crotonic and fumaric acid and maleic anhydride.
4. Pigment compositions for paper coating according to either of claims 1 or 3, characterised in that the dispersing agent has a specific viscosity lying preferentially between 0.30 and 1.0 when measured in the form of a sodium salt.
5. Pigment compositions for paper coating according to any one of claims 1 to 4, characterised in that the polyvalent salt-forming agent belongs to the group consisting of divalent and trivalent cations and is preferentially selected from calcium, magnesium, zinc, copper, lead, aluminium or chromium.
6. Pigment compositions for paper coating according to any one of claims 1 to 5, characterised in that the formation of a salt of the dispersing agent by at least one multivalent salt-forming agent takes place to a level of between 0.6 and 1.
7. Pigment compositions for paper coating according to claim 6, characterised in that the formation of a salt of the dispersing agent by at least one multivalent salt-forming agent takes place to a level of at least 0.6, the acid sites which have not formed salts remaining in the said acid state.
8. Pigment compositions for paper coating according to claim 6, characterised in that the formation of the salt of the dispersing agent by a least one multivalent salt-forming agent takes place to a level of at least 0.6, the acids sites which are still free being formed into salts by means of a monovalent salt-forming agent selected from the group consisting of lithium, sodium, potassium, ammonium and an amine.
9. Pigment compositions for paper coating according to any one of claims 1 to 8, characterised in that the dispersing agent is used in the said compositions at a concentration of 0.10 to 1.5% and preferably from 0.15 to 1% by weight with respect to the dry pigment.
10. Pigment compositions for paper coating according to any one of claims 1 to 9, characterised in that they contain, as percentages by weight with respect to the mass of anhydrous mineral pigment, in addition to the aqueous phase,
a) between 0.10 and 1.5% and preferably between 0.15 and 1.0% of the dispersing agent,
b) from 7 to 20% of a binding agent and/or water-retaining agent,
c) if applicable, the usual additives in known percentages.
11. Pigment compositions for paper coating according to any one of claims 1 to 10, characterised in that the pigments used alone or as a mixture are selected from the group consisting of kaolins, titanium oxides, talcs, natural or precipitated carbonates, aluminium hydroxides, the double hydrated sulphate of aluminium and calcium.
12. Pigment compositions for paper coating according to any one of claims 1 to 11, characterised in that the binding agent and/or water retention agent is selected from the group consisting of starch, carboxymethylcellulose, polyvinyl alcohol, styrene-butadiene and styrene-acrylate.
13. Pigment compositions for paper coating according to any one of claims 1 to 12, characterised in that they also contain various normal additives.
EP87420222A 1986-08-22 1987-08-19 Complex pigmentary compositions for coating paper Expired - Lifetime EP0261039B1 (en)

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