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US20100111809A1 - Use in a paint of a dry-ground calcium carbonate with a copolymer of (meth)acrylic acid with an alkoxy or hydroxy polyalkyleneglycol group - Google Patents

Use in a paint of a dry-ground calcium carbonate with a copolymer of (meth)acrylic acid with an alkoxy or hydroxy polyalkyleneglycol group Download PDF

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Publication number
US20100111809A1
US20100111809A1 US12/523,207 US52320708A US2010111809A1 US 20100111809 A1 US20100111809 A1 US 20100111809A1 US 52320708 A US52320708 A US 52320708A US 2010111809 A1 US2010111809 A1 US 2010111809A1
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chosen
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calcium carbonate
radical
copolymer
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US12/523,207
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Jean-Marc Suau
Jacques Mongoin
Denis Ruhlmann
Olivier Guerret
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Coatex SAS
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Coatex SAS
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Assigned to COATEX S.A.S. reassignment COATEX S.A.S. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GUERRET, OLIVIER, MONGOIN, JACQUES, RUHLMANN, DENIS, SUAU, JEAN-MARC
Publication of US20100111809A1 publication Critical patent/US20100111809A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/021—Calcium carbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/62—L* (lightness axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates

Definitions

  • the present invention concerns the field of paints, where the said paints contain at least one mineral matter which is a calcium carbonate obtained by dry grinding.
  • This grinding which leads to a reduction in the sizes of the individual particles of calcium carbonate by mechanical action, is assisted by grinding agents which can be classified into the following 3 categories.
  • the first comprises the weak acids (formic, acetic, lactic, adipic as mentioned in document FR 2 863 914, or stearic as indicated in document EP 0 510 890), and their salts (sodium lignin sulfonate, sodium acetate, etc.).
  • the second includes the weak bases, and notably the amines (see document GB 2 179 268).
  • the third and the most commonly used, since it is the most effective, includes the glycol-based alcohols, including notably diethylene glycol illustrated in documents WO 2002/081 573 and US 2003/019 399.
  • a first object of the invention consists in the use, in a paint, of a calcium carbonate characterised in that the said carbonate is dry-ground in the presence of a grinding aid agent, firstly, and in that the grinding aid agent is, secondly, a copolymer, consisting:
  • This grinding aid agent may be designated using the expression of a copolymer of methacrylic acid with a monomer containing an alcoxy or hydroxy polyalkyleneglycol group.
  • a calcium carbonate according to the invention enables a cement to be obtained with a much higher degree of spreading.
  • the said copolymer is obtained in the acidic form and possibly distilled, and is possibly partially or totally neutralised by one or more neutralisation agents having a monovalent or polyvalent cation, where the said agents are chosen preferentially from among ammonia or from among calcium, magnesium hydroxides and/or oxides, or from among sodium, potassium or lithium hydroxides, or from among the aliphatic and/or cyclic primary, secondary or tertiary amines, such as preferentially stearylamine, the ethanolamines (mono-, di- and triethanolamine), mono- and diethylamine, cyclohexylamine, methylcyclohexylamine, amino methyl propanol, morpholine, and preferentially in that the neutralisation agent is chosen from among triethanolamine and sodium hydroxide.
  • the neutralisation agent is chosen from among triethanolamine and sodium hydroxide.
  • copolymer is obtained by processes of radical polymerisation in solution, in a direct or reverse emulsion, in suspension or precipitation in solvents, in the presence of catalytic systems and chain transfer agents, or again by processes of controlled radical polymerisation, and preferentially by nitroxide mediated polymerisation (NMP) or by cobaloximes, by atom transfer radical polymerisation (ATRP), by controlled radical polymerisation by sulphurated derivatives, chosen from among carbamates, dithioesters or trithiocarbonates (RAFT) or xanthates.
  • NMP nitroxide mediated polymerisation
  • ATRP atom transfer radical polymerisation
  • sulphurated derivatives chosen from among carbamates, dithioesters or trithiocarbonates (RAFT) or xanthates.
  • the said copolymer may possibly, before or after the total or partial neutralisation reaction, be treated and separated into several phases, according to static or dynamic processes known to the skilled man in the art, by one or more polar solvents belonging preferentially to the group constituted by water, methanol, ethanol, propanol, isopropanol, the butanols, acetone and tetrahydrofuran or their blends.
  • polar solvents belonging preferentially to the group constituted by water, methanol, ethanol, propanol, isopropanol, the butanols, acetone and tetrahydrofuran or their blends.
  • One of the phases then corresponds to the polymer used according to the invention.
  • This use is also characterised in that 0.05% to 5%, preferentially 0.1% to 3%, and very preferentially 0.1% to 1%, by dry weight of the said copolymer relative to the dry weight of calcium carbonate is used during the dry grinding of the said carbonate.
  • a second purpose of the invention consists of the paints obtained by the use of dry-ground calcium carbonate according to the invention.
  • This test illustrates the prior art and uses a calcium carbonate obtained by dry grinding in the presence of 3000 ppm (relative to the dry weight of calcium carbonate) of a grinding agent of the prior art, which is diethylene glycol.
  • This test illustrates the prior art and uses a calcium carbonate obtained by dry grinding in the presence of 3000 ppm (relative to the dry weight of calcium carbonate) of a grinding agent of the invention which is a polymer consisting, by weight percentage, 81.5% of methoxy polyethylene glycol methacrylate of molecular weight 2000, 4.9% of methacrylic acid, and 13.6% of acrylic acid.
  • a grinding agent of the invention which is a polymer consisting, by weight percentage, 81.5% of methoxy polyethylene glycol methacrylate of molecular weight 2000, 4.9% of methacrylic acid, and 13.6% of acrylic acid.
  • This test illustrates the prior art and uses a calcium carbonate obtained by dry grinding in the presence of 1400 ppm (relative to the dry weight of calcium carbonate) of a grinding agent of the prior art, which is diethylene glycol.
  • This test illustrates the prior art and uses a calcium carbonate obtained by dry grinding in the presence of 1400 ppm (relative to the dry weight of calcium carbonate) of a grinding agent of the invention which is a polymer consisting, by weight percentage, 81.5% of methoxy polyethylene glycol methacrylate of molecular weight 2000, 4.9% of methacrylic acid, and 13.6% of acrylic acid.
  • a grinding agent of the invention which is a polymer consisting, by weight percentage, 81.5% of methoxy polyethylene glycol methacrylate of molecular weight 2000, 4.9% of methacrylic acid, and 13.6% of acrylic acid.
  • n° 2 and 4 The polymer used in tests n° 2 and 4 is obtained by polymerisation techniques well known to the skilled man in the art.
  • the temperature is then raised and 604.78 g is distilled.
  • the temperature is brought down to between 50 and 60° C., and 69.34 g of sodium hydroxide at 50% mass in water is added to the reactive medium.
  • the medium is diluted with 20.85 g of water. It is cooled again before obtaining the polymer of the invention.
  • the StormerTM, ICITM and BrookfieldTM viscosities were determined according to the methods well known to the skilled man in the art. Certain optical characteristics of the paints obtained were also measured, such as notably L whiteness, the “3 Hunterlab filters” Sub-tone, covering power or contrast ratio, and the level of brightness at angles equal to 60° and 85°.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Disintegrating Or Milling (AREA)

Abstract

The invention resides in the use in a paint of a calcium carbonate characterised in that it is obtained by dry-grinding, firstly, and in that it is dry-ground in the presence of a grinding aid agent which is a copolymer of (meth)acrylic acid with a monomer containing an alcoxy or hydroxy polyalkyleneglycol group, secondly. The invention also concerns the paints thus obtained.

Description

  • The present invention concerns the field of paints, where the said paints contain at least one mineral matter which is a calcium carbonate obtained by dry grinding.
  • Grinding using a dry process (as opposed to in an aqueous medium) of calcium carbonate is described in the documents “Beitrag zur Aufklärung der Wirkungsweise von Mahlhilfsmitteln” (“Freiberger Forschungshefte” VEB Deutscher Verlag für Grundstoffindustrie, Leipzig, Germany (1975)). and “Calcium Carbonate” (Birkhäuser Verlag, 2001).
  • This grinding, which leads to a reduction in the sizes of the individual particles of calcium carbonate by mechanical action, is assisted by grinding agents which can be classified into the following 3 categories.
  • The first comprises the weak acids (formic, acetic, lactic, adipic as mentioned in document FR 2 863 914, or stearic as indicated in document EP 0 510 890), and their salts (sodium lignin sulfonate, sodium acetate, etc.). The second includes the weak bases, and notably the amines (see document GB 2 179 268). The third, and the most commonly used, since it is the most effective, includes the glycol-based alcohols, including notably diethylene glycol illustrated in documents WO 2002/081 573 and US 2003/019 399.
  • Although they are still the most effective, the latter lead to calcium carbonates with a high quantity of volatile organic compounds (VOCs). For this reason, finding an alternative solution to these glycol-based grinding aid agents which is at least as effective as them in terms of the final application would constitute a major contribution to the state of the technique.
  • With this regard, a first object of the invention consists in the use, in a paint, of a calcium carbonate characterised in that the said carbonate is dry-ground in the presence of a grinding aid agent, firstly, and in that the grinding aid agent is, secondly, a copolymer, consisting:
    • a) of at least one anionic monomer chosen from among acrylic acid, methacrylic acid and their blends,
    • b) and of at least one non-ionic monomer, of formula (I):
  • Figure US20100111809A1-20100506-C00001
      • where:
        • m, n, p and q are integers such that: m, n, p≦150, q≧1, and 5≦(m+n+p)q≦150, and preferentially 15≦(m+n+p)q≦120,
        • R1 represents hydrogen or the methyl or ethyl radical,
        • R2 represents hydrogen or the methyl or ethyl radical,
        • R represents a radical containing an unsaturated polymerisable function, preferentially belonging to the group of vinylics, or to the group of acrylic, methacrylic, maleic esters, or to the group of unsaturated urethanes such as acrylurethane, methacrylurethane, α-α′ dimethyl-isopropenyl-benzylurethane, allylurethane, or to the group of allylic or vinylic ethers, whether or not substituted, or again to the group of ethylenically unsaturated amides or imides, or again to the group constituted by acrylamide and methacrylamide,
        • R′ represents hydrogen or a hydrocarbonated radical with 1 to 40 carbon atoms, preferentially 1 to 4 carbon atoms, where R′ is very preferentially the methyl radical,
      • or a blend of several monomers of formula (I),
    • c) and possibly of at least one other monomer chosen from among (meth)acrylic anhydride, (meth)acrylamide, or from among the (meth)acrylic esters, such as preferentially the acrylates and methacrylates with 1 to 20 carbon atoms in their ester radical, such as very preferentially the methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl, ter-butyl or 2-ethylhexyl acrylates, the methyl or ethyl methacrylates, the hydroxylated methacrylates such as the hydroxyethyl and hydroxypropyl methacrylates, or from among the aromatic vinylic monomers such as preferentially styrene, α-methylstyrene, styrene sulfonate, or acrylamido-2-methyl-2-propane-sulfonic acid, or from among the organophosphate monomers, such as preferentially the acrylate and methacrylate phosphates of ethylene glycol, or the acrylate and methacrylate phosphates of oxyethylene and/or oxypropylene glycol, and their blends.
  • This grinding aid agent may be designated using the expression of a copolymer of methacrylic acid with a monomer containing an alcoxy or hydroxy polyalkyleneglycol group.
  • The examples of the present Application show that, in comparison with a calcium carbonate which is dry ground with a diethylene glycol, a calcium carbonate according to the invention enables a cement to be obtained with a much higher degree of spreading.
  • This use is also characterised in that the said copolymer consists, expressed as a percentage by weight of the monomers (the sum of the percentages by weight of all the monomers equals 100%):
    • a) 0.5% to 50%, preferentially 1% to 25%, and very preferentially 5% to 20%, of at least one anionic monomer chosen from among acrylic acid, methacrylic acid and their blends,
    • b) of 50% to 99.5%, preferentially 75% to 99%, and very preferentially 80% to 95%, of at least one non-ionic monomer, of formula (I):
  • Figure US20100111809A1-20100506-C00002
      • where:
        • m, n, p and q are integers such that: m, n, p≦150, q≧1, and 5≦(m+n+p)q≦150, and preferentially 15≦(m+n+p)q≦120,
        • R1 represents hydrogen or the methyl or ethyl radical,
        • R2 represents hydrogen or the methyl or ethyl radical,
        • R represents a radical containing an unsaturated polymerisable function, preferentially belonging to the group of vinylics, or to the group of acrylic, methacrylic, maleic esters, or to the group of unsaturated urethanes such as acrylurethane, methacrylurethane, α-α′ dimethyl-isopropenyl-benzylurethane, allylurethane, or to the group of allylic or vinylic ethers, whether or not substituted, or again to the group of ethylenically unsaturated amides or imides, or again to the group constituted by acrylamide and methacrylamide,
        • R′ represents hydrogen or a hydrocarbonated radical with 1 to 40 carbon atoms, preferentially 1 to 4 carbon atoms, where R′ is very preferentially the methyl radical,
      • or a blend of several monomers of formula (I),
    • c) 0% to 50% of at least one other monomer chosen from among (meth)acrylic anhydride, (meth)acrylamide, or from among the (meth)acrylic esters, such as preferentially the acrylates and methacrylates with 1 to 20 carbon atoms in their ester radical, such as very preferentially the methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl, ter-butyl or 2-ethylhexyl acrylates, the methyl or ethyl methacrylates, the hydroxylated methacrylates such as the hydroxyethyl and hydroxypropyl methacrylates, or from among the aromatic vinylic monomers such as preferentially styrene, α-methylstyrene, styrene sulfonate, or acrylamido-2-methyl-2-propane-sulfonic acid, or from among the organophosphate monomers, such as preferentially the acrylate and methacrylate phosphates of ethylene glycol, or the acrylate and methacrylate phosphates of oxyethylene and/or oxypropylene glycol, and their blends.
  • This use is also characterised in that the said copolymer is obtained in the acidic form and possibly distilled, and is possibly partially or totally neutralised by one or more neutralisation agents having a monovalent or polyvalent cation, where the said agents are chosen preferentially from among ammonia or from among calcium, magnesium hydroxides and/or oxides, or from among sodium, potassium or lithium hydroxides, or from among the aliphatic and/or cyclic primary, secondary or tertiary amines, such as preferentially stearylamine, the ethanolamines (mono-, di- and triethanolamine), mono- and diethylamine, cyclohexylamine, methylcyclohexylamine, amino methyl propanol, morpholine, and preferentially in that the neutralisation agent is chosen from among triethanolamine and sodium hydroxide.
  • This use is also characterised in that the said copolymer is obtained by processes of radical polymerisation in solution, in a direct or reverse emulsion, in suspension or precipitation in solvents, in the presence of catalytic systems and chain transfer agents, or again by processes of controlled radical polymerisation, and preferentially by nitroxide mediated polymerisation (NMP) or by cobaloximes, by atom transfer radical polymerisation (ATRP), by controlled radical polymerisation by sulphurated derivatives, chosen from among carbamates, dithioesters or trithiocarbonates (RAFT) or xanthates. This use is also characterised in that the said copolymer may possibly, before or after the total or partial neutralisation reaction, be treated and separated into several phases, according to static or dynamic processes known to the skilled man in the art, by one or more polar solvents belonging preferentially to the group constituted by water, methanol, ethanol, propanol, isopropanol, the butanols, acetone and tetrahydrofuran or their blends.
  • One of the phases then corresponds to the polymer used according to the invention.
  • This use is also characterised in that 0.05% to 5%, preferentially 0.1% to 3%, and very preferentially 0.1% to 1%, by dry weight of the said copolymer relative to the dry weight of calcium carbonate is used during the dry grinding of the said carbonate.
  • A second purpose of the invention consists of the paints obtained by the use of dry-ground calcium carbonate according to the invention.
    • EXAMPLES
  • In these examples, all the grinding operations are undertaken according to a method well known to the skilled man in the art (document FR 2 901 491 describes such a method). We shall confine ourselves here to indicating the final granulometry of the particles of calcium carbonate obtained after grinding (the skilled man in the art in reality knows how to modify the parameters of the process with a view to obtaining such a granulometry; however, one may also refer to the above-mentioned document).
  • In each of the tests n° 1 to 4, a matt paint is produced in aqueous phase by blending whilst stirring of the different constituents, in the proportions in grams as indicated in table 1.
  • Test n° 1 2 3 4
    Prior Art (PA)/Invention (IN) PA IN PA IN
    Water 292.0 292.0 292.0 292.0
    Ammonium hydroxide (31% 2.0 2.0 2.0 2.0
    solution)
    Coatex ™ P90 (40% solution) 4.0 4.0 4.0 4.0
    Mergal ™ K6N 2.0 2.0 2.0 2.0
    Byk ™ 034 2.0 2.0 2.0 2.0
    TiO2 RL68 41.0 41.0 41.0 41.0
    Omyacoat ™ 850 OG 215.0 215.0 215.0 215.0
    CaCO3 dry ground according 328.0 0 0 0
    to test n° 1
    CaCO3 dry ground according 0 328.0 0 0
    to test n° 2
    CaCO3 dry ground according 0 0 328.0 0
    to test n° 3
    CaCO3 dry ground according 0 0 0 328.0
    to test n° 4
    Acronal ™ 290D 82.0 82.0 82.0 82.0
    Monoethylene glycol 10.0 10.0 10.0 10.0
    Texanol ™ 10.0 10.0 10.0 10.0
    Rheo ™ 3000 12.0 12.0 12.0 12.0
    Total (g) 1000.0 1000.0 1000.0 1000.0
    Coatex ™ P90 designates a thickener sold by the company COATEX ™,
    Rheo ™ 3000 designates a thickener sold by the company COATEX ™,
    Mergal ™ K6N designates a bactericide sold by the company TROY ™,
    Byk ™ 034 designates an anti-foaming agent sold by the company BYK ™,
    TiO2 RL68 designates a titanium dioxide powder sold by the company MILLENIUM ™,
    Omyacoat ™ 850 OG designates a calcium carbonate sold by the company OMYA ™,
    Acronal ™ 290 D designates a binder sold by the company BASF ™,
    Texanol ™ designates a coalescence agent sold by the company EASTMANN ™
    • Test No. 1
  • This test illustrates the prior art and uses a calcium carbonate obtained by dry grinding in the presence of 3000 ppm (relative to the dry weight of calcium carbonate) of a grinding agent of the prior art, which is diethylene glycol.
  • After grinding a calcium carbonate is obtained, 73.8% and 48.5% by weight of the particles of which have an average diameter lower respectively than 2 μm and 1 μm (as measured using a Sedigraph™ 5100).
    • Test No. 2
  • This test illustrates the prior art and uses a calcium carbonate obtained by dry grinding in the presence of 3000 ppm (relative to the dry weight of calcium carbonate) of a grinding agent of the invention which is a polymer consisting, by weight percentage, 81.5% of methoxy polyethylene glycol methacrylate of molecular weight 2000, 4.9% of methacrylic acid, and 13.6% of acrylic acid.
  • After grinding a calcium carbonate is obtained, 74.5% and 44.1% by weight of the particles of which have an average diameter lower respectively than 2 μm and 1 μm (as measured using a Sedigraph™ 5100).
    • Test No. 3
  • This test illustrates the prior art and uses a calcium carbonate obtained by dry grinding in the presence of 1400 ppm (relative to the dry weight of calcium carbonate) of a grinding agent of the prior art, which is diethylene glycol.
  • After grinding a calcium carbonate is obtained, 47.1% and 30.0% by weight of the particles of which have an average diameter lower respectively than 2 μm and 1 μM (as measured using a Sedigraph™ 5100).
    • Test No. 4
  • This test illustrates the prior art and uses a calcium carbonate obtained by dry grinding in the presence of 1400 ppm (relative to the dry weight of calcium carbonate) of a grinding agent of the invention which is a polymer consisting, by weight percentage, 81.5% of methoxy polyethylene glycol methacrylate of molecular weight 2000, 4.9% of methacrylic acid, and 13.6% of acrylic acid.
  • After grinding a calcium carbonate is obtained, 45.4% and 28.0% by weight of the particles of which have an average diameter lower respectively than 2 μm and 1 μm (as measured using a Sedigraph™ 5100).
  • The polymer used in tests n° 2 and 4 is obtained by polymerisation techniques well known to the skilled man in the art.
  • In a first beaker the following are introduced at ambient temperature and whilst stirring: 259.02 of methoxy polyethylene glycol methacrylate of molecular weight equal to 2000 g/mol, a solution containing 15.36 g of methacrylic acid and 274.39 g of water, a solution containing 69.86 g of untreated water and 50.25 g of acrylic acid
  • In a second beaker the following are introduced at ambient temperature and whilst stirring: 2.38 g of thiolactic acid (of 98.5% mass purity) and 52.14 g of water.
  • In a third beaker the following are introduced at ambient temperature and whilst stirring: 2.84 g of ammonium persulphate (NH4)2S2O8 and 51.90 g of water.
  • In a fourth beaker the following are introduced at ambient temperature and whilst stirring: 0.56 g of ammonium persulphate (NH4)2S2O8 and 10.87 g of water.
  • In a single-casing cylindrical reactor, surmounted by a refrigerating column, by an anchor stirring system and 3 inlets, 351.39 g of water and 295.61 g of isopropanol are introduced. The reactive medium is heated whilst stirring (230 rpm) to 84±2° C. The contents of the first 3 beakers are introduced into the reactive medium in 2 hours. The introduction nozzles are then rinsed with 20.84 g of water (this water goes directly into the reactive medium). The solution of the 4th beaker is then added to the reactive medium, and the blend is fired for 1 hour at 84±2° C. (at 230 rpm). At the end of the reaction the device is rinsed with 52.13 g of water. The temperature is then raised and 604.78 g is distilled. The temperature is brought down to between 50 and 60° C., and 69.34 g of sodium hydroxide at 50% mass in water is added to the reactive medium. Finally the medium is diluted with 20.85 g of water. It is cooled again before obtaining the polymer of the invention.
  • For each of the tests n° 1 to 4, the Stormer™, ICI™ and Brookfield™ viscosities were determined according to the methods well known to the skilled man in the art. Certain optical characteristics of the paints obtained were also measured, such as notably L whiteness, the “3 Hunterlab filters” Sub-tone, covering power or contrast ratio, and the level of brightness at angles equal to 60° and 85°.
  • The methods used are notably described in document FR 2 872 815.
  • The results are shown in tables 2 and 3.
  • TABLE 2
    Test Test Test Test
    Viscosities no 1 no 2 no 3 no 4
    Time t = 0 μI (P) 1.9 1.9 1.6 1.6
    μS (K · U) 102 106 99 100
    μB 10 (mPa · s) 13700 15100 11600 11100
    μB100 (mPa · s) 3300 3600 2900 3000
    Time t = 24 hours μB 10 (mPa · s) 18900 18400 12700 12300
    μB100 (mPa.s) 4900 4750 3500 3100
    Instant t = 7 days μB 10 (mPa · s) 43900 32100 15400 12800
    50° C. μB 10 (mPa.s) 14000 8340 4500 3200
    Instant t = μB 10 (mPa · s) Taken 42800 15800 13800
    1 month 50° C. μB 10 (mPa · s) in 12000 4700 3400
    mass
    μI (P): ICI ™ viscosity
    μS (K · U): Stormer ™ viscosity
    μB 10 (mPa · s): Brookfield ™ viscosity determined at 10 revolutions per minute
    μB 100 (mPa · s): Brookfield ™ viscosity determined at 100 revolutions per minute
  • TABLE 3
    Test n° 1 2 3 4
    Whiteness.
    Measurement of the “L” 99.2 99.1 98.7 98.6
    “3 Hunterlab filters” Sub-tone
    Value of b 2.2 2.3 2.3 2.2
    Covering power of dry film
    Contrast ratio
    RC = Yn/Yb 96.9% 96.8% 96.0% 95.9%
    Level of brightness
    t = 72 h
    60° 4.7 4.6 4.8 4.7
    85° 32.9 33.5 14.9 15.6
  • By comparing the tests 2 by 2 (1 to 2, and 3 to 4), it is observed that the optical properties of the paint films are in the context of the invention at the same level as for the prior art.
  • Conversely, a clear drift of the Brookfield™ viscosity is observed in the case of paints formulated according to the prior art. At the same time, this viscosity remains much more stable in the context of the invention.
  • We have therefore succeeded in developing a dry-ground calcium carbonate which, in the paint field, has a more stable Brookfield viscosity, without modifying the optical properties of the dry film.

Claims (7)

1. A calcium carbonate for use in a paint which is dry-ground in the presence of a copolymer grinding aid agent comprising:
a) at least one anionic monomer chosen from acrylic acid, methacrylic acid and their blends,
b) at least one non-ionic monomer, of formula (I):
Figure US20100111809A1-20100506-C00003
where:
m, n, p and q are integers such that: m, n, p≦150, q≧1, and 5≦(m+n+p)q≦150,
R1 represents hydrogen or the methyl or ethyl radical,
R2 represents hydrogen or the methyl or ethyl radical,
R represents a radical containing an unsaturated polymerisable function chosen from the group of vinylics, the group of acrylic, methacrylic, and maleic esters, the group of unsaturated urethanes selected from the group consisting of acrylurethane, methacrylurethane, α-α′ dimethyl-isopropenyl-benzylurethane, and allylurethane, the group of allylic or vinylic ethers, whether or not substituted, the group of ethylenically unsaturated amides or imides, and the group consisting of acrylamide and methacrylamide, and
R′ represents hydrogen or a hydrocarbonated radical with 1 to 40 carbon atoms,
or a blend of several monomers of formula (I),
c) and optionally at least one other monomer chosen from (meth)acrylic anhydride and (meth)acrylamide, the esters chosen from the acrylates and methacrylates with 1 to 20 carbon atoms in their ester radical, and the hydroxylated methacrylates chosen from the hydroxyethyl and hydroxypropyl methacrylates, the aromatic vinylic monomers chosen from styrene, α-methylstyrene, and styrene sulfonate, and acrylamido-2-methyl-2-propane-sulfonic acid, the organophosphate monomers chosen from the acrylate and methacrylate phosphates of ethylene glycol, and the acrylate and methacrylate phosphates of oxyethylene and/or oxypropylene glycol, and their blends.
2. The calcium carbonate according to claim 1, wherein said copolymer comprises, expressed as a percentage by weight of the monomers in which the sum of the percentages by weight of all the monomers equals 100%:
a) 0.5% to 50% of at least one anionic monomer chosen from acrylic acid, methacrylic acid and their blends,
b) 50% to 99.5%, of at least one non-ionic monomer, of formula (I):
Figure US20100111809A1-20100506-C00004
where:
m, n, p and q are integers such that: m, n, p≦150, q≧1 and 5≦(m+n+p)q≦150,
R1 represents hydrogen or the methyl or ethyl radical,
R2 represents hydrogen or the methyl or ethyl radical,
R represents a radical containing an unsaturated polymerisable function chosen from the group of vinylics, the group of acrylic, methacrylic, maleic, itaconic, crotonic, and vinylphthalic esters, the group of unsaturated urethanes selected from the group consisting of acrylurethane, methacrylurethane, α-α′ dimethyl-isopropenyl-benzylurethane, and allylurethane, the group of allylic and vinylic ethers, whether or not substituted, the group of ethylenically unsaturated amides or imides, and the group consisting of acrylamide and methacrylamide, and
R′ represents hydrogen or a hydrocarbonated radical with 1 to 40 carbon atoms,
or a blend of several monomers of formula (I), and
c) 0% to 50% of at least one other monomer chosen from (meth)acrylic anhydride and (meth)acrylamide, the esters chosen from the acrylates and methacrylates with 1 to 20 carbon atoms in their ester radical, and the hydroxylated methacrylates selected from the hydroxyethyl and hydroxypropyl methacrylates, the aromatic vinylic monomers chosen from styrene, α-methylstyrene, and styrene sulfonate, and acrylamido-2-methyl-2-propane-sulfonic acid, the organophosphate monomers chosen from the acrylate and methacrylate phosphates of ethylene glycol, and the acrylate and methacrylate phosphates of oxyethylene and/or oxypropylene glycol, and their blends.
3. The calcium carbonate according to claim 1, wherein said copolymer is obtained in the acidic form and optionally distilled, and is optionally partially or totally neutralised by one or more neutralisation agents having a monovalent or polyvalent cation, where said agents are chosen from ammonia and calcium and magnesium hydroxides and/or oxides, sodium, potassium and lithium hydroxides, and the aliphatic and/or cyclic primary, secondary or tertiary amines chosen from stearylamine, the ethanolamines, mono- and diethylamine, cyclohexylamine, methylcyclohexylamine, amino methyl propanol, and morpholine.
4. The calcium carbonate according to claim 1, wherein said copolymer is obtained by a polymerization process chosen from of radical polymerisation in solution, in a direct or reverse emulsion, in suspension or precipitation in solvents, in the presence of catalytic systems and chain transfer agents, or a process of controlled radical polymerisation, chosen from nitroxide mediated polymerisation (NMP) or cobaloximes, atom transfer radical polymerisation (ATRP), and controlled radical polymerisation by sulphurated derivatives, chosen from carbamates, dithioesters or trithiocarbonates (RAFT) or xanthates.
5. The calcium carbonate according to claim 3, wherein said copolymer is, before or after the total or partial neutralisation reaction, treated and separated into several phases, according to static or dynamic processes, by one or more polar solvents selected from the group consisting of water, methanol, ethanol, propanol, isopropanol, the butanols, acetone, tetrahydrofuran and their blends.
6. The calcium carbonate according to claim 1, wherein 0.05% to 5% by dry weight of the said copolymer relative to the dry weight of calcium carbonate is used during the dry grinding of the said carbonate.
7. A paint obtained by use of the dry-ground calcium carbonate according to claim 1.
US12/523,207 2007-03-05 2008-02-26 Use in a paint of a dry-ground calcium carbonate with a copolymer of (meth)acrylic acid with an alkoxy or hydroxy polyalkyleneglycol group Abandoned US20100111809A1 (en)

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
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CN102827524A (en) * 2012-08-23 2012-12-19 吴燕湘 Water-based coating composition
US8445579B2 (en) 2007-03-05 2013-05-21 Coatex S.A.S. Use in a paint of a dry-ground calcium carbonate with a copolymer of (meth)acrylic acid with an alkoxy or hydroxy polyalkyleneglycol group
US8445561B2 (en) 2007-03-05 2013-05-21 Coatex S.A.S. Use in a hydraulic binder composition of a dry-ground calcium carbonate with a copolymer of (meth)acrylic acid and an alkoxy or hydroxy polyalkyleneglycol group
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Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK2455429T3 (en) * 2010-11-19 2013-11-25 Omya Int Ag Process for preparing aqueous suspensions of mineral materials using amines combined with vinyl carboxyl polymers
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KR102858549B1 (en) * 2019-02-26 2025-09-12 옴야 인터내셔널 아게 Method for producing surface-treated calcium carbonate material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4013602A (en) * 1972-10-09 1977-03-22 Pluss-Staufer Ag Ultrafine natural calcium carbonates as fillers in varnishes and paints
US5145902A (en) * 1989-08-04 1992-09-08 Coatex S.A. Application to aqueous calcium carbonate pigment suspensions of a polycarboxylic agent with phosphoric or phosphonic groups which inhibit the shock effect caused by the introduction of an electrolyte at high concentration
US20040019148A1 (en) * 2000-06-15 2004-01-29 Jean-Marc Suau Use of weakly anionic copolymers as dispersing and/or grinding aid agent of an aqueous suspension of mineral materials
US20090312459A1 (en) * 2006-05-24 2009-12-17 Gane Patrick A C Method for Dry Grinding a Material Containing a Carbonate Ore

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07100141B2 (en) 1987-12-10 1995-11-01 東亞合成株式会社 Dry grinding aid
JPH10338518A (en) * 1997-06-03 1998-12-22 Kurimoto Ltd Production of calcium carbonate
US6414065B1 (en) * 1999-11-05 2002-07-02 Celanese International Corporation Multifunctional poly(vinyl alcohol) binder for fine particle size calcium carbonate pigment
FR2913428B1 (en) 2007-03-05 2009-06-05 Coatex Soc Par Actions Simplif USE IN PAINT, DRY CAULK CALCIUM CARBONATE WITH COPOLYMER OF (METH) ACRYLIC ACID WITH ALCOXY OR HYDROXY POLYALKYLENE GLYCOL FUNCTION.
FR2913426B1 (en) 2007-03-05 2009-06-05 Coatex Soc Par Actions Simplif USE AS A RHEOLOGY AGENT IN A LOADED PLASTIC PULP, A DRY CURED CARBONATE WITH A COPOLYMER OF (METH) ACRYLIC ACID WITH AN ALCOXY OR HYDROXY POLYALKYLENE GLYCOL FUNCTION.
FR2913420B1 (en) 2007-03-05 2009-05-01 Coatex Soc Par Actions Simplif USE IN HYDRAULIC BINDER COMPOSITION, DRY-CURED CALCIUM CARBONATE WITH COPOLYMER OF (METH) ACRYLIC ACID, AND ALCOXY OR HYDROXY POLYALKYLENE GLYCOL FUNCTION.

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4013602A (en) * 1972-10-09 1977-03-22 Pluss-Staufer Ag Ultrafine natural calcium carbonates as fillers in varnishes and paints
US5145902A (en) * 1989-08-04 1992-09-08 Coatex S.A. Application to aqueous calcium carbonate pigment suspensions of a polycarboxylic agent with phosphoric or phosphonic groups which inhibit the shock effect caused by the introduction of an electrolyte at high concentration
US20040019148A1 (en) * 2000-06-15 2004-01-29 Jean-Marc Suau Use of weakly anionic copolymers as dispersing and/or grinding aid agent of an aqueous suspension of mineral materials
US20090312459A1 (en) * 2006-05-24 2009-12-17 Gane Patrick A C Method for Dry Grinding a Material Containing a Carbonate Ore

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8445579B2 (en) 2007-03-05 2013-05-21 Coatex S.A.S. Use in a paint of a dry-ground calcium carbonate with a copolymer of (meth)acrylic acid with an alkoxy or hydroxy polyalkyleneglycol group
US8445561B2 (en) 2007-03-05 2013-05-21 Coatex S.A.S. Use in a hydraulic binder composition of a dry-ground calcium carbonate with a copolymer of (meth)acrylic acid and an alkoxy or hydroxy polyalkyleneglycol group
CN103380180A (en) * 2010-12-13 2013-10-30 太阳化学公司 Process for Solubilizing Grinding Media in Pigment Particle Dispersions
US9617409B2 (en) 2010-12-13 2017-04-11 Sun Chemical Corporation Methods of solubilizing milling media in pigment particle dispersions
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US10889661B2 (en) 2010-12-17 2021-01-12 Basf Se Stable polyacrylic acids, their manufacture and their use
US9309153B2 (en) 2012-04-27 2016-04-12 Halliburton Energy Services, Inc. Wide temperature range cement retarder
US9422194B2 (en) 2012-04-27 2016-08-23 Halliburton Energy Services, Inc. Wide temperature range cement retarder
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CN102827524B (en) * 2012-08-23 2014-08-27 吴燕湘 Water-based coating composition

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