EP0261039A1 - Komplexe Pigmentzusammensetzungen für die Papierbeschichtung - Google Patents

Komplexe Pigmentzusammensetzungen für die Papierbeschichtung Download PDF

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Publication number
EP0261039A1
EP0261039A1 EP87420222A EP87420222A EP0261039A1 EP 0261039 A1 EP0261039 A1 EP 0261039A1 EP 87420222 A EP87420222 A EP 87420222A EP 87420222 A EP87420222 A EP 87420222A EP 0261039 A1 EP0261039 A1 EP 0261039A1
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EP
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Prior art keywords
compositions
agent
coating
dispersing agent
pigment
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EP87420222A
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English (en)
French (fr)
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EP0261039B1 (de
Inventor
Olivier Gonnet
Jean Vallas
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Coatex SAS
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Société COATEX Société Anonyme
Coatex SAS
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Priority to AT87420222T priority Critical patent/ATE59069T1/de
Publication of EP0261039A1 publication Critical patent/EP0261039A1/de
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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 state ionic phase of the aqueous phase and that, during their preparation and mixing prior to the coating of the paper and / or their storage, the already mentioned increase in viscosities and the solidification in certain cases of said compositions is manifested, in especially 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 consisting of a polymer and / or copolymer of ethylenic acids whose acid functions 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 from 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 especially 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
  • 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.
  • complex pigment compositions it is intended to define all the pigment formulations containing a pigment at a higher concentration than prior art or a mixture of several pigments whose incompatibility is evident in the presence of a dispersing agent of the prior art.
  • pigments used in the context of the invention alone or as a mixture mention may be made of kaolins, titanium oxides, talcs, natural or precipitated carbonates, aluminum hydroxides, satin white (double sulfate aluminum and hydrated calcium), natural or synthetic gypsum.
  • 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 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 following monomers: acrylic, methacrylic, itaconic, 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, methylvin
  • 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 even dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, hexane, heptane, benzene, toluene, xylene, acetic acids, tartaric, lactic, citric, gluconic, glucoheptonic, 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 specific viscosity of the carboxylic polymers and / or copolymers which is symbolized by the letter " ⁇ " 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.
  • 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 precise measurements of specific viscosity. precision.
  • the salifying agent having a versatile 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.
  • Table I 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 amount of dispersing agent.
  • test 3 In a second group of tests (tests 3 and 4), a pH interval was studied for a given concentration of dispersing agent, this interval 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.
  • 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.
  • 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 TiO2 (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 with sodium ion.
  • TiO2 titanium dioxide Anatase from THANN AND MULHOUSE
  • dispersing agents acrylic polymers
  • Tests 6 to 24 relate to pigmentary compositions for coating the paper conform to the invention, comprising 72% by weight of TiO2 (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.
  • TiO2 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 TiO2) 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 TiO2) 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
  • 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.
  • 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 coating paper were prepared according to known methods (tests 25 to 27, TiO2 AHR of TIOXIDE and tests 28 to 30, TiO2 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 per Ca2+ and at a rate of 0.3 per 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 per Ca2+ and at a rate of 0.3 per Na+
  • 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 have been 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 rate of 0.3 per Na+ introduced into said compositions according to increasing rates.
  • 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 rate of 0.3 per Na+ introduced into said compositions according to increasing rates.
  • 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 as dry / dry, 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 pigmentary compositions for coating paper using 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 of 7 m2 / g: test 35) or precipitated calcium carbonate (Socal P3 from SOLVAY: test 37, with a BET specific surface area of 14 m2 / g) in the presence of a dispersing agent (above-mentioned acrylic polymer) which, according to the prior art, is completely salified with sodium ion.
  • natural calcium carbonate from OMYA with a specific surface BET of 7 m2 / g: test 35
  • precipitated calcium carbonate Socal P3 from SOLVAY: test 37, with a BET specific surface area of 14 m2 / g
  • a dispersing agent above-mentioned acrylic polymer
  • Tests 36 and 38 relate to aqueous pigmentary 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 ( aforementioned acrylic polymer) which, according to the invention, is salified at a rate of 0.7 per Ca2+ and a rate of 0.3 per Na+.
  • a dispersing agent aforementioned acrylic polymer
  • tests 35 and 37 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.
  • 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.
  • TiO2 titanium dioxide Anatase from THANN AND MULHOUSE
  • 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.
  • 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+).
  • 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).
  • 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.
  • 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.
  • 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
  • the coating compositions were subjected to Brookfield viscosity measurements at rotational speeds of 10 rpm and 100 rpm with an appropriate mobile.
  • 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.
  • 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.
  • 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.
  • the coating compositions thus prepared were subjected to Brookfield viscosity measurements at rotational speeds of 10 rpm and 100 rpm
EP87420222A 1986-08-22 1987-08-19 Komplexe Pigmentzusammensetzungen für die Papierbeschichtung Expired - Lifetime EP0261039B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87420222T ATE59069T1 (de) 1986-08-22 1987-08-19 Komplexe pigmentzusammensetzungen fuer die papierbeschichtung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8612099 1986-08-22
FR8612099A FR2603042B1 (fr) 1986-08-22 1986-08-22 Compositions pigmentaires complexes pour l'enduction du papier

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Publication Number Publication Date
EP0261039A1 true EP0261039A1 (de) 1988-03-23
EP0261039B1 EP0261039B1 (de) 1990-12-12

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US (1) US4775420A (de)
EP (1) EP0261039B1 (de)
JP (1) JPS6359497A (de)
AR (1) AR242618A1 (de)
AT (1) ATE59069T1 (de)
AU (1) AU604251B2 (de)
BR (1) BR8704323A (de)
CA (1) CA1289288C (de)
DE (1) DE3766679D1 (de)
ES (1) ES2019965B3 (de)
FI (1) FI89190C (de)
FR (1) FR2603042B1 (de)
ZA (1) ZA875892B (de)

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WO1992019685A1 (en) * 1991-05-08 1992-11-12 Engelhard Corporation Composite titania-calcined kaolin opacifying pigments and method for making and using same
EP0542644A1 (de) * 1991-11-12 1993-05-19 Coatex S.A. Mahl- und/oder Dispersionshilfsmittel auf Basis von Polymeren und/oder teilweise durch Magnesium neutralisierten Kopolymeren für wässerige Suspensionen von mineralen Materialien, welche sich eignen für pigmentäre Anwendungen
EP0542643A1 (de) * 1991-11-12 1993-05-19 Coatex S.A. Mahl- und/oder Dispersionshilfsmittel auf Basis von Polymeren und/oder teilweise durch Magnesium neutralisierten Kopolymeren für wässerige Suspensionen von mineralen Materialien, welche sich eignen für pigmentäre Anwendungen
EP2194103A1 (de) 2008-12-04 2010-06-09 Omya Development Ag Verfahren zur Herstellung von Calciumcarbonatmaterialien mit einer Teilchenoberfläche mit verbesserten Adsorptionseigenschaften
EP2199348A1 (de) 2008-12-19 2010-06-23 Omya Development AG Verfahren zur Herstellung von wässrigen Suspensionen von mineralischen Materialien oder getrockneten mineralischen Materialien, erhaltendes Produkt und Verwendungen dafür
EP2390284A1 (de) 2010-05-28 2011-11-30 Omya Development AG Verfahren zur Herstellung von hochfesten Suspensionen aus Mineralmaterialien
EP2712895A1 (de) 2012-09-26 2014-04-02 Omya International AG Rheologisch stabile wässrige Mineralmaterialsuspensionen mit organischen Polymeren mit reduziertem VOC-Gehalt
EP2910609A1 (de) 2014-02-21 2015-08-26 Omya International AG Verfahren zur Herstellung eines Kalziumkarbonatprodukts

Families Citing this family (33)

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JPH0717864B2 (ja) * 1987-02-12 1995-03-01 有限会社三好化成 保湿性粉体および化粧料
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FR2683536B1 (fr) * 1991-11-12 1993-12-31 Coatex Sa Agent de broyage et/ou de dispersion a base de polymeres et/ou copolymeres neutralises en partie par du magnesium pour suspensions aqueuses de materiaux mineraux en vue d'applications pigmentaires.
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FR2785629B1 (fr) 1998-11-10 2000-12-22 Coatex Sa Composition polymerique retenteur d'eau et activateur d'azurants optiques, sauces de couchage pour papier, et feuilles de papier couche ainsi obtenues
FR2796403B1 (fr) * 1999-07-16 2001-09-28 Coatex Sa Nouvel agent de retention d'eau hydrosoluble en milieu neutre ou alcalin de type copolymere vinylique-acrylique, applications aux sauces de couchage pour papier et carton, et sauces de couchage et papiers et cartons ainsi obtenus
FR2818165B1 (fr) 2000-12-20 2003-10-31 Coatex Sas Agent d'aide au broyage de materiaux mineraux en suspension aqueuse. suspensions aqueuses obtenues et leurs utilisations
FR2818166B1 (fr) 2000-12-20 2003-10-31 Coatex Sas Agent d'aide au broyage et/ou de dispersion de materiaux mineraux en suspension aqueuse. suspensions aqueuses obtenues et leurs utilisations
DE60229851D1 (de) * 2001-05-18 2008-12-24 Sun Chemical Corp Verfahren zum anfärben von cellulosematerialien unter verwendung einer kationischen pigmentdispersion
FR2846972B1 (fr) * 2002-11-08 2005-02-18 Omya Ag Suspensions aqueuses de matieres minerales broyees, faiblement chargees ioniquement et leurs utilisations
FR2864455B1 (fr) * 2003-12-24 2006-03-17 Coatex Sas Utilisation de polymeres hydrosolubles structures obtenus par polymerisation radicalaire controlee comme dispersant et agent d'aide au broyage de matieres minerales
EP1752499A1 (de) 2005-07-25 2007-02-14 Omya Development AG Verfahren zur Dispergieren und oder Zerkleinern und oder Konzentrieren von Calcium Carbonat in wässrigem Medium, mittels einer wässrigen Lösung enthaltend Zirkonienverbindungen.
JP5207097B2 (ja) * 2006-06-16 2013-06-12 星光Ｐｍｃ株式会社 填料改質剤、填料スラリー及び製紙方法
JP5113784B2 (ja) 2008-03-31 2013-01-09 ローム アンド ハース カンパニー （メタ）アクリル酸のホモポリマーおよび／またはコポリマーを含む分散剤を使用して水性分散物中で鉱物を粉砕する方法
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WO1992019685A1 (en) * 1991-05-08 1992-11-12 Engelhard Corporation Composite titania-calcined kaolin opacifying pigments and method for making and using same
EP0542644A1 (de) * 1991-11-12 1993-05-19 Coatex S.A. Mahl- und/oder Dispersionshilfsmittel auf Basis von Polymeren und/oder teilweise durch Magnesium neutralisierten Kopolymeren für wässerige Suspensionen von mineralen Materialien, welche sich eignen für pigmentäre Anwendungen
EP0542643A1 (de) * 1991-11-12 1993-05-19 Coatex S.A. Mahl- und/oder Dispersionshilfsmittel auf Basis von Polymeren und/oder teilweise durch Magnesium neutralisierten Kopolymeren für wässerige Suspensionen von mineralen Materialien, welche sich eignen für pigmentäre Anwendungen
US5432238A (en) * 1991-11-12 1995-07-11 Coatex S.A. Grinding and/or dispersing agent containing polymers and/or copolymers partially neutralized by magnesium for aqueous suspensions of mineral substances, to be used in pigmentary applications
US9879139B2 (en) 2008-12-04 2018-01-30 Omya International Ag Process for manufacturing calcium carbonate materials having a particle surface with improved adsorption properties
EP2194103A1 (de) 2008-12-04 2010-06-09 Omya Development Ag Verfahren zur Herstellung von Calciumcarbonatmaterialien mit einer Teilchenoberfläche mit verbesserten Adsorptionseigenschaften
US9896567B2 (en) 2008-12-04 2018-02-20 Omya International Ag Process for manufacturing calcium carbonate materials having a particle surface with improved adsorption properties
EP2199348A1 (de) 2008-12-19 2010-06-23 Omya Development AG Verfahren zur Herstellung von wässrigen Suspensionen von mineralischen Materialien oder getrockneten mineralischen Materialien, erhaltendes Produkt und Verwendungen dafür
US9969888B2 (en) 2008-12-19 2018-05-15 Omya International Ag Process for manufacturing aqueous suspensions of mineral materials or dried mineral materials, the obtained products, as well as uses thereof
US10472522B2 (en) 2008-12-19 2019-11-12 Omya International Ag Process for manufacturing aqueous suspensions of mineral materials or dried mineral materials, the obtained products, as well as uses thereof
EP2390284A1 (de) 2010-05-28 2011-11-30 Omya Development AG Verfahren zur Herstellung von hochfesten Suspensionen aus Mineralmaterialien
WO2011147922A1 (en) 2010-05-28 2011-12-01 Omya Development Ag Process for manufacturing high solids suspensions of mineral materials
US8721838B2 (en) 2010-05-28 2014-05-13 Omya International Ag Process for manufacturing high solids suspensions of mineral materials
US9243121B2 (en) 2010-05-28 2016-01-26 Omya International Ag Process for manufacturing high solids suspensions of mineral materials
EP2712895A1 (de) 2012-09-26 2014-04-02 Omya International AG Rheologisch stabile wässrige Mineralmaterialsuspensionen mit organischen Polymeren mit reduziertem VOC-Gehalt
EP2910609A1 (de) 2014-02-21 2015-08-26 Omya International AG Verfahren zur Herstellung eines Kalziumkarbonatprodukts
US10119032B2 (en) 2014-02-21 2018-11-06 Omya International Ag Process for the preparation of a mineral filler product

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US4775420A (en) 1988-10-04
ZA875892B (en) 1988-02-12
FI89190C (fi) 1993-08-25
EP0261039B1 (de) 1990-12-12
AR242618A1 (es) 1993-04-30
AU7668387A (en) 1988-02-25
FR2603042A1 (fr) 1988-02-26
BR8704323A (pt) 1988-04-19
DE3766679D1 (de) 1991-01-24
FI873622A (fi) 1988-02-23
JPS6359497A (ja) 1988-03-15
FI89190B (fi) 1993-05-14
AU604251B2 (en) 1990-12-13
ATE59069T1 (de) 1990-12-15
FR2603042B1 (fr) 1988-11-10
FI873622A0 (fi) 1987-08-21
CA1289288C (fr) 1991-09-17
ES2019965B3 (es) 1991-07-16

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