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WO2024240172A2 - Aqueous binder compositions and water-borne coating compositions comprising the same - Google Patents

Aqueous binder compositions and water-borne coating compositions comprising the same Download PDF

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Publication number
WO2024240172A2
WO2024240172A2 PCT/CN2024/094649 CN2024094649W WO2024240172A2 WO 2024240172 A2 WO2024240172 A2 WO 2024240172A2 CN 2024094649 W CN2024094649 W CN 2024094649W WO 2024240172 A2 WO2024240172 A2 WO 2024240172A2
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Prior art keywords
weight
monomers
range
monomer
binder composition
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PCT/CN2024/094649
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French (fr)
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WO2024240172A3 (en
Inventor
Zhen Wei
Ling Qing PENG
Jing Miao DAI
Li Feng Liu
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BASF China Co Ltd
BASF SE
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BASF China Co Ltd
BASF SE
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Priority to CN202480021912.9A priority Critical patent/CN120882814A/en
Publication of WO2024240172A2 publication Critical patent/WO2024240172A2/en
Publication of WO2024240172A3 publication Critical patent/WO2024240172A3/en
Anticipated expiration legal-status Critical
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    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Definitions

  • the present invention relates to aqueous binder compositions comprising an aqueous polymer latex of a carboxylated polymer and a polyetheramine polyol.
  • the present invention also relates to water-borne coating compositions containing an aqueous binder composition according to the present invention.
  • polymer latex and “polymer dispersion” are used as synonyms and means an aqueous polymer composition of a water-insoluble polymer, where the polymer is present in the form of finely dispersed polymer particles.
  • the polymer latex is obtainable by emulsion polymerization (also termed primary latex) but it may also be obtainable by emulsifying a polymer in an aqueous phase (secondary latex) .
  • branching points may be tri or tetra-substituted carbon atoms and/or tertiary amino groups.
  • the branching points are in particular the tertiary amino groups.
  • the polyetheramine polyol contains on average from 1 to 8.2 mol/kg of tertiary amino groups.
  • the polyetheramine polyol contains on average from 2 to 8.0 mol/kg of tertiary amino groups, especially from 4 to 7.9 mol/kg.
  • the polyetheramine polyol may contain hydroxyl groups.
  • the OH number of the polyetheramine polyol is frequently at least 100 mg KOH/g, e.g., 100 to 800 mg KOH/g, in particular at least 200 mg KOH/g, e.g., 200 to 700 mg KOH/g, especially at least 250 mg KOH/g, e.g., 250 to 650 mg KOH/g, determined according to DIN 53240, part 2.
  • the number of hydroxyl groups per molecule will depend on the number average molecular weight of the polyetheramine polyol and the degree of branching.
  • the number average molecular weight, M n , of the polyetheramine polyol is frequently in the range of from 500 to 155000 g/mol, in particular in the range from 1000 to 60000 g/mol, such as 5000 g/mol, 10000 g/mol, 20000 g/mol, 30000 g/mol, 40000 g/mol, 50000 g/mol, 60000 g/mol, 70000 g/mol, 80000 g/mol, 90000 g/mol, 100000 g/mol, 110000 g/mol, 120000 g/mol, 130000 g/mol, 140000 g/mol, 150000 g/mol, determined by gel permeation chromatography using hexafluoroisopropanol as the mobile phase and polymethylmethacrylate as a standard.
  • the polyetheramine polyol is frequently amorphous and thus may show a glass transition.
  • the glass transition temperature of the polyetheramine polyol does not exceed 50°C, more preferably, it does not exceed 30°C and more preferably not exceed 10°C, determined by differential scanning calorimetry (DSC) , as described below.
  • the glass transition temperature of the polyetheramine polyol is preferably in the range of-55 to 30°C and more preferably in the range of-55 to 10°C, determined by DSC.
  • Polyetheramine polyols and their preparation are known, for example from DE 3206459, EP 441 198, WO 2009/047269, WO 2014/012812, which disclose polyetheramine polyols based on a polycondensation product of at least one trialkanolamine.
  • the polyetheramine polyol is obtainable by polycondensation of at least one trialkanolamine or by polycondensation of a mixture of at least one trialkanolamine with an aliphatic or cycloaliphatic polyol.
  • trialkanolamines are preferably selected from tri-C 2 -C 8 -alkanol amines, wherein the alkanol groups in trialkanolamine may be different or identical, wherein the alkanol groups are preferably identical. More preferably, the trialkanolamines are selected from tri-C 2 -C 4 -alkanol amines, wherein the alkanol groups are identical.
  • trialkanolamines are triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, and triisobutanolamine and mixtures thereof.
  • aliphatic diols are polyether diols of the general formula HO- ( (CH 2 ) n -O) m -H with n being independently from each other 1 to 10, preferably 2 to 4 and m being in the range of 2 to 100.
  • the polyether diols are selected from polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymers thereof.
  • polyols having more than 2 hydroxyl groups are glycerol, pentaerythritol, trimethylolpropane, sorbitol, and the like.
  • the polyols may also be alkoxylated, in particular ethoxylated or propoxylated, e.g., ethoxylated glycerol, propoxylated glycerol, ethoxylated pentaerythritol, propoxylated pentaerythritol, ethoxylated trimethylolpropane, propoxylated trimethylolpropane, ethoxylated sorbitol and propoxylated sorbitol.
  • ethoxylated or propoxylated e.g., ethoxylated glycerol, propoxylated glycerol, ethoxylated pentaerythritol, propoxylated pentaerythritol, ethoxylated trimethylolpropane, propoxylated trimethylolpropane, ethoxylated sorbitol and propoxylated sorbitol.
  • the polyetheramine polyol is preferably obtainable by polycondensation of monomers containing 50 to 100 mol%of compounds selected from trialkanolamines and 0 to 50 mol%of compounds selected from aliphatic or cycloaliphatic polyols, preferably containing 70 to 100 mol%of compounds selected from trialkanolamines and 0 to 30 mol%of compounds selected from aliphatic or cycloaliphatic polyols, more preferably containing 80 to 100 mol%of compounds selected from trialkanolamines and 0 to 20 mol%of compounds selected from aliphatic or cycloaliphatic polyols, whereby “mol%” are based on the total amount of monomers.
  • the polyetheramine polyol is obtainable by polycondensation, wherein monomers consist only of monomers selected from trialkanolamines.
  • the trialkanolamine is preferably selected from tri-C 2 -C 4 -alkanolamines.
  • Preferred tri-C 2 -C 4 -alkanolamines are selected from triethanolamine, triisopropanolamine, and tri-n-propanolamine.
  • the mixture of at least one trialkanolamine with an aliphatic or cycloaliphatic polyol is preferably selected form mixtures of at least one trialkanolamine, which is selected from the group consisting of tri-C 2 -C 4 -alkanolamines, and an aliphatic or cycloaliphatic C 2 -C 8 -polyol.
  • polyetheramine polyols obtainable by polycondensation of either triethanolamine, or of triisopropanolamine, or of a mixture of triethanolamine and triisopropanolamine.
  • at least one further polyol, in particular at least one further diol might be present.
  • the polycondensation can be carried out with or without the presence of a catalyst.
  • Suitable catalysts include but are not limited to phosphoric acid (H 3 PO 4 ) , phosphorous acid (H 3 PO 3 ) or hypophosphoric acid (H 3 PO 2 ) , which can be applied in bulk or as aqueous solution.
  • the catalyst is added in an amount of from 0.001 to 10 mol%, preferably from 0.005 to 7 mol%, more preferably from 0.01 to 5 mol%, based on the amount of the trialkanolamine.
  • the polycondensation can be carried out by using a solvent.
  • solvents aromatic and/or (cyclo) aliphatic hydrocarbons and their mixtures, halogenated hydrocarbons, ketones, esters, and ethers.
  • aromatic hydrocarbons (cyclo) aliphatic hydrocarbons, alkyl esters of alkanoic acids, ketones, alkoxylated alkyl esters of alkanoic acids, and mixtures thereof.
  • Particularly preferred are monoalkylated or polyalkylated benzenes and naphthalenes, ketones, alkyl esters of alkanoic acids, and alkoxylated alkyl esters of alkanoic acids and mixtures thereof.
  • the polycondensation is preferably carried out without using a solvent.
  • the polycondensation can be carried out in a way that the temperature during polycondensation does not exceed 250°C and preferably not exceed 230°C.
  • the polycondensation is carried out at temperatures in the range of from 150 to 230°C, preferably 180 to 215°C. Even more preferably, the temperature during polycondensation does not exceed 215°C and especially not exceed 210°C.
  • the polycondensation can be carried out at a pressure in the range of from 0.02 to 20 bar. Preferably, the polycondensation is carried out at normal pressure.
  • the polycondensation is preferably followed by removal or blow-off of residual monomers, for example by distilling them off at normal pressure or at reduced pressure, for example, in the range of from 0.1 to 0.5 bar.
  • Water or other volatile products that are released during the polycondensation can be removed from the reaction mixture in order to accelerate the reaction.
  • water or other volatile products that are released during the polycondensation are removed, such removal being accomplished by distillation, for example, and optionally under reduced pressure.
  • the removal of water or of other low molecular mass reaction by-products can also be assisted by passing through the reaction mixture a stream of gas which is substantially inert under the reaction conditions (stripping) , such as nitrogen, for example, or a noble gas such as helium, neon, or argon, for example.
  • the polyetheramine polyols described herein are typically stable at room temperature for a prolonged period, such as for at least 10 weeks, for example.
  • the polyetheramine polyols are stable without exhibiting instances of clouding, precipitation, and/or significant increase in viscosity.
  • the polycondensation can be terminated by a variety of options.
  • the temperature can be lowered to a range in which the reaction comes to a standstill and the polycondensation product is storage-stable. This is generally the case below 100°C, preferably below 60°C, more preferably below 40°C, and very preferably at room temperature.
  • Another option is to deactivate the catalyst by adding a basic component, a Lewis base or an organic or inorganic base, for example.
  • the polycondensation can be carried out in stirred tank reactors or stirred tank reactor cascades. The process can be carried out batch-wise, in semi-batch mode or continuously.
  • Polycondensation products of trialkanolamines and poly-co-condensation products of trialkanolamines as described herein are preferably used as polyetheramine polyol without chemical modification or derivatization.
  • a derivative of a polycondensation product of trialkanolamines or a derivative of a poly-co-condensation product of a trialkanolamine can be used instead of a non-derivatized polycondensation or poly-co-condensation product.
  • Derivatives of such polycondensation and poly-co-condensation products of trialkanolamines include products obtained by alkoxylation of the hydroxyl end groups of the non-derivatized polycondensation and poly-co-condensation products.
  • the amino groups of the polycondensation and poly-co-condensation products can also be quaternized to obtain permanently cationic modified polymers by use of alkylating agents.
  • the polyetheramine polyol usually dissolves readily in a variety of solvents, such as water, alcohols, such as methanol, ethanol, n-butanol, alcohol/water mixtures, acetone, 2-butanone, ethyl acetate, butyl acetate, methoxypropyl acetate, methoxyethyl acetate, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene carbonate, or propylene carbonate.
  • solvents such as water, alcohols, such as methanol, ethanol, n-butanol, alcohol/water mixtures, acetone, 2-butanone, ethyl acetate, butyl acetate, methoxypropyl acetate, methoxyethyl acetate, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene carbonate, or propylene
  • the aqueous binder composition usually contains the polyetheramine polyol in the composition in an amount from 0.01 to 10%by weight, in particular from 0.05 to 7.5%by weight, more particular from 0.1 to 5%by weight based on the dry weight of the carboxylated polymer of the aqueous polymer latex.
  • the aqueous binder composition of the invention also contains an aqueous polymer latex of a carboxylated polymer, also referred as a film forming carboxylated polymer.
  • film forming in the context of the polymer latex means the ability of the carboxylated polymer of the polymer latex to form a film on surfaces upon drying under application conditions.
  • the polymer will frequently have a film forming temperature of at most 50°C, in particular at most 30°C.
  • the film forming temperature may be lowered, for example by addition of film forming aids, such as plasticizers and solvents.
  • the capability of the polymer of the latex to be film forming under application conditions will depend on its glass transition temperature.
  • the carboxylated polymer of the aqueous polymer dispersions has a glass transition temperature T g in the range from -20 to +60°C, in particular from 0 to +50°C, especially in the range from +5 to +40°C.
  • the glass transition temperature can be determined by the DSC method (differential scanning calorimetry, 20 K/min, midpoint measurement) in accordance to DIN 53765: 1994-03 or ISO 1 1357-2, with sample preparation preferably to DIN EN ISO 16805: 2005.
  • the glass transition temperatures of the individual polymer phases may be outside the ranges given here.
  • the weight average glass transition temperature T g (av) as calculated by the equation T g (av) (T g (1) *w 1 + T g (2) *w 2 ....T g (n) *w n )
  • T g (1) , T g (2) to T g (n) indicate the individual glass transition temperatures in K of the individual polymers 1, 2 to n while w 1 , w 2 to w n indicate the amount in %by weight of the individual polymers 1, 2 to n. If the polymer of the aqueous polymer dispersions contains polymers having different Tg′s, the difference between the lowest T g and the highest T g may be as high as e.g., 100°C, e.g. from 10 to 100°C.
  • the polymer dispersed in the aqueous polymer dispersion has only one T g , or, if it contains polymers having different T g ′s, the maximum difference of the lowest T g and the highest T g does not exceed 50 K, in particular 20 K.
  • Tg 1 , Tg 2 ,...., Tg n are the glass transition temperatures in degrees Kelvin of the polymers synthesized from only one of the monomers 1, 2,...., n at a time.
  • the Tg values for the homopolymers of most monomers are known and listed, for example, in Ullmann’s Encyclopedia of Industrial Chemistry, 5th ed., vol. A21, page 169, Verlag Chemie, Weinheim, 1992; further sources of glass transition temperatures of homopolymers are, for example, J. Brandrup, E.H. Immergut, Polymer Handbook, 1 st Ed., J. Wiley, New York 1966, 2nd Ed. J. Wiley, New York 1975, and 3rd Ed. J. Wiley, New York 1989.
  • the glass transition temperature of the one phase is usually above 40°C, preferably at least 60°C, determined via DSC as described herein.
  • the glass transition temperature of the other phase, according to Fox, is usually below 40°C, preferably at most 30°C, determined via DSC as described herein.
  • the polymer preferably contains 95 to 40%by weight, based on the total weight of the polymer, of the polymer with the lower glass transition temperature, which is usually below 40°C, and 5 to 60%by weight, based on the total weight of the polymer, of the polymer with the higher glass transition temperature, which is usually above 40°C.
  • carboxylated polymer means that the polymer of the latex bears carboxyl groups attached to the polymer backbone.
  • carboxyl groups are incorporated into the polymer by means of polymerized ethylenically unsaturated monomers having one or more carboxyl group.
  • Such monomers are typically selected from monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms and monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms. Examples of such monomers are acrylic acid, methacrylic acid, crotonic acid, 2-ethylpropenoic acid, 2-propylpropenoic acid, itaconic acid, and fumaric acid.
  • the carboxylated polymer of the polymer latex is usually obtainable by a radical copolymerization of a monomers M forming the carboxylated monomer latex.
  • monomers M which are also termed monomer composition M, comprise at least one monoethylenically unsaturated monomer having at least one carboxyl group, which is, for example, selected from monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms and monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, and at least one further neutral ethylenically unsaturated monomer, which is essentially water insoluble, i.e.
  • said monomer composition comprises from 0.05 to 10%by weight, based on the total weight of the monomers contained in the monomer composition, of one or more monoethylenically unsaturated monomer having at least one carboxyl group.
  • the energy consumption (heat) for the carboxylated polymer synthesis is lower.
  • the reaction temperature of the synthesis is generally below 80°C, preferably below 70°C, more preferably at 60°C or below.
  • the monomer composition M essentially consists of
  • ethylenically unsaturated monomers M1 which have a solubility in deionized water of at most 50 g/l at 20°C and which are in particular selected C 1 -C 20 -alkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, di-C 1 -C 20 -alkyl esters of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, C 5 -C 20 -cycloalkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, vinylesters of C 1 -C 20 -alkanoic acids, vinyl aromatic monomers, C 2 -C 6 -monoolefines and conjugated dienes;
  • ethylenically unsaturated monomers M2 which are selected from ethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms and ethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms;
  • the term “essentially consists of” means that the total amount of monomers M1, M2 and M3 makes up at least 95%by weight, in particular at least 99%by weight or 100%by weight of the total amount of monomers of the monomer composition.
  • Examples of monomers M1 include, but are not limited to
  • - C 1 -C 20 -alkyl esters of acrylic acid such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, 2-propylheptyl acrylate, lauryl acrylate, C 12 /C 14 -alkyl acrylate, and stearyl acrylate,
  • acrylic acid such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-butyl acrylate, isobutyl acrylate, n-pent
  • -C 1 -C 20 -alkylesters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, n-decyl methacrylate, 2-propylheptyl methacrylate, lauryl methacrylate, C 12 /C 14 -alkyl methacrylate, and stearyl methacrylate;
  • methacrylic acid such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl
  • -di-C 1 -C 20 -alkyl esters of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms such as di-C 1 -C 20 -alkyl esters of itaconic acid, di-C 1 -C 20 -alkyl esters of citraconic acid, di-C 1 -C 20 -alkyl esters of maleic acid and di-C 1 -C 20 -alkyl esters of fumaric acid,
  • At least one monomer M1a selected from C 1 -C 20 -alkyl esters of acrylic acid, C 5 -C 20 -alkylesters of methacrylic acid and mixtures thereof; and
  • Suitable monomers M1a are
  • - C 1 -C 20 -alkyl esters of acrylic acid such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, 2-propylheptyl acrylate, lauryl acrylate, C 12 /C 14 -alkyl acrylate, and stearyl acrylate;
  • - C 5 -C 20 -alkylesters of methacrylic acid such as n-pentyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, n-decyl methacrylate, 2-propylheptyl methacrylate, lauryl methacrylate, C 12 /C 14 -alkyl methacrylate, and stearyl methacrylate;
  • Suitable monomers M1b are
  • - C 1 -C 4 -alkyl esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-butyl methacrylate, isobutyl methacrylate and tert. -butyl methacrylate, with particular preference given to methyl methacrylate;
  • - vinyl aromatic monomers in particular mono-vinyl substituted aromatic hydrocarbons such as styrene, 2-methylstyrene, 4-methylstyrene, 2-n-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and alpha-methylstyrene, with particular preference given to styrene;
  • monomers M1a are selected from C 2 -C 10 -alkyl esters of acrylic acid, in particular from ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, and 2-propylheptyl acrylate.
  • monomers M1b are selected from vinyl aromatic monomers and C 1 -C 4 -alkyl esters of methacrylic acid and mixtures thereof, in particular from styrene, methyl methacrylate.
  • the relative amount of M1a and M1b may vary in particular from 10 ⁇ 1 to 1 ⁇ 10 by weight, more particularly from 5 ⁇ 1 to 1 ⁇ 5 by weight, especially from 3 ⁇ 1 to 1 ⁇ 3 by weight, such as 9 ⁇ 1, 8 ⁇ 1, 7 ⁇ 1, 8 ⁇ 1, 5 ⁇ 1, 4 ⁇ 1, 3 ⁇ 1, 2 ⁇ 1, 1 ⁇ 1, 2 ⁇ 1, 3 ⁇ 1, 4 ⁇ 1, 5 ⁇ 1, 6 ⁇ 1, 7 ⁇ 1, 8 ⁇ 1, 9 ⁇ 1 by weight, etc.
  • the amount of M1 used according to the present invention is in the range from 70%by weight to 99.95%by weight, such as 70%by weight, 75%by weight, 80%by weight, 85%by weight, 90%by weight, 95%by weight, 99%by weight, etc., based on the total weight of the monomer composition M.
  • monomers M2 include, but are not limited to acrylic acid, methacrylic acid, crotonic acid, 2-ethylpropenoic acid, 2-propylpropenoic acid, itaconic acid and fumaric acid or a mixture thereof.
  • monomers M2 is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, 2-ethylpropenoic acid, 2-propylpropenoic acid, itaconic acid and fumaric acid and a mixture thereof.
  • the monomer M2 is selected from methacrylic acid or a mixture of acrylic acid and methacrylic acid.
  • the amount of M2 used according to the present invention is in the range from 0.5%by weight to 10%by weight, such as 1%by weight, 2%by weight, 3%by weight, 4%by weight, 5%by weight, 6%by weight, 7%by weight, 8%by weight, 9%by weight, etc., based on the total weight of the monomer composition M.
  • Examples of monomers M3 include, but are not limited to
  • N-N-C 1 -C 10 alkyl amides of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms (monomers M3.2)
  • N-C 1 -C 10 alkyl amides of acrylic acid or methacrylic acid such as N-methyl acrylamide, N-ethyl acrylamide, N-propyl acrylamide, N-isopropyl acrylamide, N-butyl acrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-propyl methacrylamide, N-isopropyl methacrylamide and N-butyl methacrylamide;
  • - monoethylenically unsaturated monomers bearing urea or keto groups such as 2- (2-oxo-imidazolidin-1-yl) ethyl (meth) acrylate, 2-ureido (meth) acrylate, N- [2- (2-oxooxazolidin-3-yl) ethyl] methacrylate, acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, 2- (acetoacetoxy) ethyl methacrylate, diacetoneacrylamide (DAAM) and diacetonemethacrylamide;
  • DAAM diacetoneacrylamide
  • hydroxyalkyl esters of monoethylenically unsaturated C 3 -C 6 monocarboxylic acids especially hydroxyalkyl esters of acrylic acid and hydroxyalkyl esters of methacrylic acid, also referred to hereinafter as hydroxyalkyl (meth) acrylates, in particular hydroxy-C 2 -C 4 -alkylesters of acrylic acid and hydroxy-C 2 -C 4 -alkylesters of methacrylic acid, such as 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, etc.
  • monoethylenically unsaturated monomers which bear at least one tri-C 1 -C 4 -alkoxysilane group (monomers M3.5) , such as vinyl trimethoxysilane, vinyl triethoxysilane, methacryloxyethyl trimethoxysilane, methacryloxyethyl triethoxysilane, and mixtures thereof.
  • the amount of said monomers M3.5 will frequently be in the range from 0.01 to 1 pphm.
  • Monomers M3 may also include a small amount of multiethylenically unsaturated monomers (monomers M3.6) , i.e., monomers having at least 2 non-conjugated ethylenically unsaturated double bounds.
  • monomers M3.6 multiethylenically unsaturated monomers
  • the amounts of said monomers M3.6 will generally not exceed 1 pphm.
  • suitable monomers M3.6 include:
  • diesters of monoethylenically unsaturated C 3 -C 6 monocarboxylic acids with saturated aliphatic or cycloaliphatic diols in particular diesters of acrylic acid or methacrylic acid, such as the diacrylates and the dimethacrylates of ethylene glycol (1, 2-ethanediol) , propylene glycol (1, 2-propanediol) , 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, neopentyl glycol (2, 2-dimethyl-1, 3-propanediol) or 1, 2-cyclohexanediol;
  • monoesters of monoethylenically unsaturated C 3 -C 6 monocarboxylic acids with monoethylenically unsaturated aliphatic or cycloaliphatic monohydroxy compounds such as the acrylates and the methacrylates of vinyl alcohol (ethenol) , allyl alcohol (2 propen-1-ol) , 2-cyclohexen-1-ol or norbornenol; and
  • divinyl aromatic compounds such as 1, 3-divinyl benzene, 1, 4-divinyl benzene;
  • the monomers M do not contain monomers M3.6 or contain no more than 0.1 pphm of monomers M3.6.
  • hydroxyalkyl esters of acrylic acid and hydroxyalkyl esters of methacrylic acid preference is given to hydroxy-C 2 -C 4 -alkylesters of acrylic acid and hydroxy-C 2 -C 4 -alkylesters of methacrylic acid, acrylamide, methacrylamide, and to mixtures thereof.
  • the carboxylated polymer is preferably obtainable by polymerization of a monomer composition M via a redox initiator system, where the monomer composition M essentially consists of
  • the carboxylated polymer is in particular obtainable by a polymerization of a monomer composition M via a redox initiator system, where the monomer composition M consists of
  • ethylenically unsaturated monomers M1 which are selected from the group consisting of at least one monomer M1 a, selected from C 1 -C 20 -alkyl esters of acrylic acid, C 5 -C 20 -alkylesters of methacrylic acid and mixtures thereof; and at least one monomer M1b, selected from vinyl aromatic monomers, and C 1 -C 4 -alkyl esters of methacrylic acid and mixtures thereof,
  • ethylenically unsaturated monomers M2 which are selected from the group consisting of ethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms and ethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms;
  • the film forming carboxylated polymer is obtainable by a polymerization of a monomer composition M via a redox initiator system, where the monomer composition M essentially consists of
  • an aqueous binder composition comprises
  • carboxylated polymer is obtainable by a radical emulsion polymerization of a monomer composition M via a redox initiator system, where the monomer composition M comprises:
  • ethylenically unsaturated monomers M1 which are selected from C 1 -C 20 -alkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, di-C 1 -C 20 -alkyl esters of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, C 5 -C 20 -cycloalkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, vinylesters of C 1 -C 20 -alkanoic acids, vinyl aromatic monomers, C 2 -C 6 -monoolefines and conjugated dienes; and
  • ethylenically unsaturated monomers M2 which are selected from monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms and monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms,
  • the redox initiator system is present in a total amount in the range from 0.1%by weight to 2.5%by weight, in particular in the range from 0.15%by weight to 2%by weight, more particular in the range from 0.2 %by weight to 1.5%by weight based on the total weight of the monomer composition M, and
  • the redox initiator system comprises oxidizing agent and reducing agent in a weight ratio in the range from 1: 1 to 10: 1, in particular in the range from 1: 1 to 5: 1, more particular in the range from 1.1: 1 to 3: 1.
  • an aqueous binder composition comprises
  • carboxylated polymer is obtainable by a radical emulsion polymerization of a monomer composition M via a redox initiator system, where the monomer composition M comprises:
  • ethylenically unsaturated monomers M1 which are a mixture of at least one monomer M1a, selected from C 1 -C 20 -alkyl esters of acrylic acid, C 5 -C 20 -alkylesters of methacrylic acid and mixtures thereof; and at least one monomer M1b, selected from vinyl aromatic monomers, and C 1 -C 4 -alkyl esters of methacrylic acid and mixtures thereof; and
  • ethylenically unsaturated monomers M2 which are selected from ethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms,
  • the redox initiator system is present in a total amount in the range from 0.1%by weight to 2.5%by weight, in particular in the range from 0.15%by weight to 2%by weight, more particular in the range from 0.2 %by weight to 1.5%by weight based on the total weight of the monomer composition M, and
  • the redox initiator system comprises oxidizing agent and reducing agent in a weight ratio in the range from 1: 1 to 10: 1, in particular in the range from 1: 1 to 5: 1, more particular in the range from 1.1: 1 to 3: 1.
  • an aqueous binder composition comprises
  • carboxylated polymer is obtainable by a radical emulsion polymerization of a monomer composition M via a redox initiator system, where the monomer composition M comprises:
  • the redox initiator system is present in a total amount in the range from 0.1%by weight to 2.5%by weight, in particular in the range from 0.15%by weight to 2%by weight, more particular in the range from 0.2 %by weight to 1.5%by weight based on the total weight of the monomer composition M, and
  • the redox initiator system comprises oxidizing agent and reducing agent in a weight ratio in the range from 1: 1 to 10: 1, in particular in the range from 1: 1 to 5: 1, more particular in the range from 1.1: 1 to 3: 1.
  • an aqueous binder composition comprises
  • carboxylated polymer is obtainable by a radical emulsion polymerization of a monomer composition M via a redox initiator system, where the monomer composition M comprises:
  • the redox initiator system is present in a total amount in the range from 0.1%by weight to 2.5%by weight, in particular in the range from 0.15%by weight to 2%by weight, more particular in the range from 0.2 %by weight to 1.5%by weight based on the total weight of the monomer composition M, and
  • the redox initiator system comprises oxidizing agent and reducing agent in a weight ratio in the range from 1: 1 to 10: 1, in particular in the range from 1: 1 to 5: 1, more particular in the range from 1.1: 1 to 3: 1, and
  • the redox initiator system is a combination of tert-butyl hydroperoxide (TBHP) and sodium formaldehyde sulfoxylate (SFS) , a combination of tert-Amyl hydroperoxide (TAHP) and sodium formaldehyde sulfoxylate (SFS) or a combination of tert-butyl hydroperoxide (TBHP) and sodium-acetone bisulfite (SAB) .
  • TBHP tert-butyl hydroperoxide
  • SAB sodium-acetone bisulfite
  • the dispersed polymers are in the form of polymer particles.
  • the polymer particles typically have an average diameter in the range from 50 to 500 nm, in particular in the range from 60 to 400 nm and especially in the range from 80 to 300 nm.
  • the average particle diameter as referred herein relates to the Z average particle diameter as determined by means of photon correlation spectroscopy (PCS) , also known as quasielastic light scattering (QELS) or dynamic light scattering (DLS) .
  • PCS photon correlation spectroscopy
  • QELS quasielastic light scattering
  • DLS dynamic light scattering
  • the aqueous dilution may have a polymer concentration in the range from 0.001 to 0.5%by weight, depending on the particle size. For most purposes, a proper concentration will be 0.01%by weight. However, higher or lower concentrations may be used to achieve an optimum signal/noise ratio.
  • the dilution can be achieved by addition of the polymer latex to water or an aqueous solution of a surfactant in order to avoid flocculation.
  • dilution is performed by using a 0.1%by weight aqueous solution of a non-ionic emulsifier, e.g., an ethoxylated C16/C18 alkanol (degree of ethoxylation of 18) , as a diluent.
  • a non-ionic emulsifier e.g., an ethoxylated C16/C18 alkanol (degree of ethoxylation of 18)
  • Measurement configuration HPPS from Malvern, automated, with continuous-flow cuvette and Gilson autosampler. Parameters: measurement temperature 20.0°C; measurement time 120 seconds (6 cycles each of 20 s) ; scattering angle 173°; laser wavelength 633 nm (HeNe) ; refractive index of medium 1.332 (aqueous) ; viscosity 0.9546 mPa-s.
  • the measurement gives an average value of the second order cumulant analysis (mean of fits) , i.e
  • the polymers in the polymer dispersion have a narrow particle size distribution.
  • the particle size distribution is characterized by the polydispersity index, which is a dimensionless number calculated from a simple 2 parameter fit to the correlation data of the cumulant analysis. The calculation is normally done as described in ISO 13321: 1996. Frequently, the PDI will be less than 0.2.
  • the polymer latex of the carboxylated polymer is usually obtainable by an aqueous radical emulsion polymerization, in particular by free-radical aqueous emulsion polymerization, of the monomers M forming the carboxylated monomer latex by analogy to well-known processes of radical emulsion polymerisation technology, for example from the prior art cited at the outset and from “Emulsionspolymerisation” [Emulsion Polymerization] in Encyclopedia of Polymer Science and Engineering, vol. 8, pages 659 ff. (1987) ; D. C. Blackley, in High Polymer Latices, vol. 1, pages 35 ff. (1966) ; H.
  • the free-radically initiated aqueous emulsion polymerization is triggered by means of a redox initiator system.
  • Suitable oxidizing agents for the redox initiator systems can be inorganic peroxides, such as hydrogen peroxide or peroxodisulfates, such as the mono-or di-alkali metal or ammonium salts of peroxodisulfuric acid, for example the mono-and disodium, -potassium or ammonium salts, such as sodium persulfate (NaPs) , or organic peroxides such as alkyl hydroperoxides, for example tert-butyl hydroperoxide (TBHP) , tert-Amyl hydroperoxide (TAHP) , p-menthyl hydroperoxide or cumyl hydroperoxide, and also dialkyl or diaryl peroxides, such as di-tert-butyl or di-cumyl peroxide.
  • inorganic peroxides such as hydrogen peroxide or peroxodisulfates, such as the mono-or di-alkali metal or ammonium
  • Corresponding reducing agents which may be used for the redox initiator systems are sulfur compounds with a low oxidation state, such as alkali metal sulfites, for example potassium and/or sodium sulfite, alkali metal hydrogensulfites, for example potassium and/or sodium hydrogensulfite such as NaHSO3, alkali metal metabisulfites, for example potassium and/or sodium metabisulfite such as sodium metabisulfite (SMBS) , sodium-acetone bisulfite (SAB) , formaldehydesulfoxylates, for example potassium and/or sodium formaldehydesulfoxylate such as sodium formaldehyde sulfoxylate (SFS) , alkali metal salts, specifically potassium and/or sodium salts of aliphatic sulfinic acids and alkali metal hydrogensulfides, for example potassium and/or sodium hydrogensulfide, salts of polyvalent metals, such as iron (Il) sulfate, iron (I
  • the oxidizing agents and the reducing agents for the redox initiator systems can be a combination of tert-butyl hydroperoxide (TBHP) and sodium formaldehyde sulfoxylate (SFS) , a combination of tert-amyl hydroperoxide (TAHP) and sodium formaldehyde sulfoxylate (SFS) , a combination of tert-butyl hydroperoxide (TBHP) and sodium-acetone bisulfite (SAB) , etc.
  • TBHP tert-butyl hydroperoxide
  • SAB sodium-acetone bisulfite
  • the amount of the redox initiator system is present in a total amount in the range from 0.1%by weight to 2.5%by weight, preferably in the range from 0.15%by weight to 2%by weight, in particular in the range from 0.2 %by weight to 1.5%by weight, such as 0.3 %by weight, 0.4 %by weight, 0.5 %by weight, 0.6 %by weight, 0.7 %by weight, 0.8 %by weight, 0.9 %by weight, 1.0 %by weight, 1.1%by weight, 1.2 %by weight, 1.3 %by weight, 1.4 %by weight, 1.5 %by weight, 1.6 %by weight, 1.7 %by weight, 1.8 %by weight, 1.9 %by weight, 2.0 %by weight, 2.1%by weight, 2.2 %by weight, 2.3 %by weight, 2.4 %by weight, etc. based on the total weight of the monomer composition M.
  • the redox initiator system comprises oxidizing agent and reducing agent in a weight ratio in the range from 1: 1 to 10: 1, in particular in the range from 1: 1 to 5: 1, more particular in the range from 1.1: 1 to 3: 1.
  • the oxidizing agent can be present in an amount in the range from 0.09%by weight to 1.6%by weight, in particular in the range from 0.12%by weight to 1.3%by weight, more particular in the range from 0.15%by weight to 1%by weight based on the total weight of the monomer composition M, such as 0.1%by weight, 0.16%by weight, 0.2%by weight, 0.3%by weight, 0.4%by weight, 0.5%by weight, 0.6%by weight, 0.7%by weight, 0.8%by weight, 0.9%by weight, 1.1%by weight, 1.2%by weight, 1.4%by weight, 1.5%by weight, etc.
  • the reducing agent is present in an amount in the range from 0.01%by weight to 0.9%by weight, in particular in the range from 0.03%by weight to 0.7%by weight, more particular in the range from 0.05%by weight to 0.5%by weight, based on the total weight of the monomer composition M, such as 0.06%by weight, 0.1%by weight, 0.15%by weight, 0.2%by weight, 0.3%by weight, 0.4%by weight, 0.5%by weight, 0.6%by weight, 0.8%by weight, etc.
  • the amount of the redox initiator system required in the process of the invention for the emulsion polymerization can be initially charged in the polymerization vessel completely. However, it is also possible to charge none of or merely a portion of the redox initiator, for example not more than 30%by weight, especially not more than 20%by weight, based on the total amount of the redox initiator required in the aqueous polymerization medium and then, under polymerization conditions, during the free-radical emulsion polymerization of the monomer composition M to add the entire amount or any remaining residual amount, according to the consumption, batchwise in one or more portions or continuously with constant or varying flow rates.
  • the radical emulsion polymerization of the monomers forming the carboxylated polymer latex is performed by a so-called feed process, which means that at least 90%, in particular at least 95%or the total amount of the monomers to be polymerised are metered to the polymerisation reaction under polymerisation conditions during a metering period P.
  • the duration of the period P may depend on the production equipment and may vary from e.g., 20 minutes to 12 hours. Frequently, the duration of the period P will be in the range from 0.5 hour to 5 hours, especially from 1 hour to 4 hours.
  • polymerization conditions is generally understood to mean those temperatures and pressures under which the free-radically initiated aqueous emulsion polymerization proceeds at sufficient polymerization rate. They depend particularly on the redox initiator used.
  • the type and amount of the redox initiator, polymerization temperature and polymerization pressure are selected such that a sufficient amount of initiating radicals is always present to initiate or to maintain the polymerization reaction.
  • the redox initiator system is used in an amount high enough to allow over 99%of the monomer composition M is polymerized by redox initiation.
  • a seed latex is a polymer latex which is present in the aqueous polymerization medium before the metering of the monomers M is started.
  • the seed latex may help to better adjust the particle size or the final polymer latex obtained in the free-radical emulsion polymerization of the invention.
  • every polymer latex may serve as seed latex.
  • the Z average particle diameter of the polymer particles of the seed latex is preferably in the range from 10 to 80 nm, in particular from 10 to 50 nm.
  • the polymer particles of the seed latex are made of ethylenically unsaturated monomers, which comprise at least 95%by weight, based on the total weight of the monomers forming the seed latex, of one or more monomers M1a and/or M1b as defined above.
  • the polymer particles of the seed latex particularly comprise at least 95%by weight, based on the total weight of the monomers forming the seed latex, of at least one monomer M1b or of a mixture of at least one monomer M1b and one or more monomers M1a, where the proportion of monomers M1b to M1a is at least 1: 2 on a weight basis.
  • the seed latex is usually charged into the polymerisation vessel before the metering of the monomers M is started.
  • the seed latex is charged into the polymerisation vessel followed by establishing the polymerization conditions, e.g., by heating the mixture to polymerization temperature. It may be beneficial to charge at least a portion of the redox initiator into the polymerisation vessel before the metering of the monomers M is started. However, it is also possible to meter the monomers and the free-radical polymerization initiator in parallel to the polymerization vessel.
  • the amount of seed latex, calculated as solids, may frequently be in the range from 0.1 to 10%by weight, in particular from 0.5 to 5%by weight, based on the total weight of the monomers M to be polymerized.
  • the free-radical aqueous emulsion polymerization of the invention can be conducted at temperatures in the range from 0 to 170°C. Temperatures employed are generally in the range from 30 to 120°C, frequently from 40 to 100°C and often from 40 to 60°C.
  • the free-radical aqueous emulsion polymerization of the invention can be conducted at a pressure of less than, equal to or greater than 1 atm (atmospheric pressure) , and so the polymerization temperature may exceed 100°C and may be up to 170°C.
  • Polymerization of the monomers is normally performed at ambient pressure but it may also be performed under elevated pressure. In this case, the pressure may assume values of 1.2, 1.5, 2, 5, 10, 15 bar (absolute) or even higher values. If emulsion polymerizations are conducted under reduced pressure, pressures of 950 mbar, frequently of 900 mbar and often 850 mbar (absolute) are established.
  • Chain transfer agents are understood to mean compounds that transfer free radicals and which reduce the molecular weight of the polymer or control chain growth in the polymerization.
  • chain transfer agents are aliphatic and/or araliphatic halogen compounds, for example n-butyl chloride, n-butyl bromide, n-butyl iodide, methylene chloride, ethylene dichloride, chloroform, bromoform, bromotrichloromethane, dibromodichloromethane, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide, organic thio compounds, such as primary, secondary or tertiary aliphatic thiols, for example ethanethiol, n-propanethiol, 2-propanethiol, n-butanethiol, 2-butanethio
  • the total amount of chain transfer agents optionally used in the process of the invention will generally not exceed 1%by weight. However, it is possible, that during a certain period of the polymerization reaction the amount of chain transfer agent added to the polymerization reaction may exceed the value of 1%by weight, based on the total amount of monomers already added to the polymerization reaction.
  • the free-radical emulsion polymerization of the invention is usually performed in an aqueous polymerization medium, which, as well as water, comprises at least one surface-active substance (surfactant) for stabilizing the emulsion of the monomers and the polymer particles of the polymer latex.
  • an aqueous polymerization medium which, as well as water, comprises at least one surface-active substance (surfactant) for stabilizing the emulsion of the monomers and the polymer particles of the polymer latex.
  • the surfactant may be selected from emulsifiers and protective colloids.
  • Protective colloids as opposed to emulsifiers, are understood to mean polymeric compounds having molecular weights above 2000 Daltons, whereas emulsifiers typically have lower molecular weights.
  • the surfactants may be anionic or nonionic or mixtures of non-ionic and anionic surfactants.
  • Anionic surfactants usually bear at least one anionic group, which is selected from phosphate, phosphonate, sulfate, and sulfonate groups.
  • the anionic surfactants, which bear at least one anionic group are typically used in the form of their alkali metal salts, especially of their sodium salts or in the form of their ammonium salts.
  • anionic surfactants are anionic emulsifiers, in particular those, which bear at least one sulfate or sulfonate group.
  • anionic emulsifiers which bear at least one phosphate or phosphonate group may be used, either as sole anionic emulsifiers or in combination with one or more anionic emulsifiers, which bear at least one sulfate or sulfonate group.
  • anionic emulsifiers which bear at least one sulfate or sulfonate group, are, for example,
  • the salts especially the alkali metal and ammonium salts, of alkyl sulfates, especially of C 8 -C 22 -alkyl sulfates,
  • the salts especially the alkali metal and ammonium salts, of sulfuric monoesters of ethoxylated alkanols, especially of sulfuric monoesters of ethoxylated C 8 -C 22 -alkanols, preferably having an ethoxylation level (EO level) in the range from 2 to 40,
  • the salts especially the alkali metal and ammonium salts, of sulfuric monoesters of ethoxylated alkylphenols, especially of sulfuric monoesters of ethoxylated C 4 -C 18 -alkylphenols (EO level preferably 3 to 40) ,
  • the salts especially the alkali metal and ammonium salts, of alkylsulfonic acids, especially of C 8 -C 22 -alkylsulfonic acids,
  • the salts especially the alkali metal and ammonium salts, of dialkyl esters, especially di-C 4 -C 18 -alkyl esters of sulfosuccinic acid,
  • the salts especially the alkali metal and ammonium salts, of alkylbenzenesulfonic acids, especially of C 4 -C 22 -alkylbenzenesulfonic acids, and
  • the salts especially the alkali metal and ammonium salts, of mono-or disulfonated, alkyl-substituted diphenyl ethers, for example of bis (phenylsulfonic acid) ethers bearing a C 4 -C 24 -alkyl group on one or both aromatic rings.
  • the latter are common knowledge, for example from US-A-4, 269, 749, and are commercially available, for example as 2A1 (Dow Chemical Company) .
  • anionic surfactants are anionic emulsifiers, which are selected from the following groups:
  • the salts especially the alkali metal and ammonium salts, of alkyl sulfates, especially of C 8 -C 22 -alkyl sulfates,
  • the salts especially the alkali metal salts, of sulfuric monoesters of ethoxylated alkanols, especially of sulfuric monoesters of ethoxylated C 8 -C 22 -alkanols, preferably having an ethoxylation level (FO level) in the range from 2 to 40, of sulfuric monoesters of ethoxylated alkylphenols, especially of sulfuric monoesters of ethoxylated C 4 -C 18 -alkylphenols (EO level preferably 3 to 40) , of alkylbenzenesulfonic acids, especially of C 4 -C 22 -alkylbenzenesulfonic acids, and of mono-or disulfonated, alkyl-substituted diphenyl ethers, for example of bis (phenylsulfonic acid) ethers bearing a C 4 -C 24 -alkyl group on one or both aromatic rings.
  • FO level ethoxylation level
  • anionic emulsifiers which bear a phosphate or phosphonate group
  • salts selected from the following groups:
  • the salts especially the alkali metal and ammonium salts, of mono-and dialkyl phosphates, especially C 8 -C 22 -alkyl phosphates,
  • the salts, especially the alkali metal and ammonium salts, of phosphoric monoesters of C 2 -C 3 -alkoxylated alkanols preferably having an alkoxylation level in the range from 2 to 40, especially in the range from 3 to 30, for example phosphoric monoesters of ethoxylated C 8 -C 22 -alkanols, preferably having an ethoxylation level (EO level) in the range from 2 to 40, phosphoric monoesters of propoxylated C 8 -C 22 -alkanols, preferably having a propoxylation level (PO level) in the range from 2 to 40, and phosphoric monoesters of ethoxylated-co-propoxylated C 8 -C 22 -alkanols, preferably having an ethoxylation level (EO level) in the range from 1 to 20 and a propoxylation level of 1 to 20,
  • the salts especially the alkali metal and ammonium salts, of phosphoric monoesters of ethoxylated alkylphenols, especially phosphoric monoesters of ethoxylated C 4 -C 18 -alkylphenols (EO level preferably 3 to 40) ,
  • the salts especially the alkali metal and ammonium salts, of alkylphosphonic acids, especially C 8 -C 22 -alkylphosphonic acids and
  • the salts especially the alkali metal and ammonium salts, of alkylbenzenephosphonic acids, especially C 4 -C 22 -alkylbenzenephosphonic acids.
  • the surfactant comprises at least one anionic emulsifier, which bears at least one sulfate or sulfonate group.
  • the at least one anionic emulsifier which bears at least one sulfate or sulfonate group, may be the sole type of anionic emulsifiers.
  • mixtures of at least one anionic emulsifier, which bears at least one sulfate or sulfonate group, and at least one anionic emulsifier, which bears at least one phosphate or phosphonate group may also be used.
  • the amount of the at least one anionic emulsifier, which bears at least one sulfate or sulfonate group is preferably at least 50%by weight, based on the total weight of anionic surfactants used in the process of the present invention.
  • the amount of anionic emulsifiers, which bear at least one phosphate or phosphonate group does not exceed 20%by weight, based on the total weight of anionic surfactants used in the process of the present invention.
  • the surfactant may also comprise one or more nonionic surface-active substances, which are especially selected from nonionic emulsifiers.
  • Suitable nonionic emulsifiers are e. g., araliphatic or aliphatic nonionic emulsifiers, for example ethoxylated mono-, di-and trialkylphenols (EO level: 3 to 50, alkyl radical: C 4 -C 10 ) , ethoxylates of long-chain alcohols (EO level: 3 to 100, alkyl radical: C 8 -C 36 ) , and polyethylene oxide/polypropylene oxide homo-and copolymers.
  • alkylene oxide units may comprise the alkylene oxide units copolymerized in random distribution or in the form of blocks.
  • Very suitable examples are the EO/PO block copolymers.
  • Preference is given to ethoxylates of long-chain alkanols, in particular to those where the C 8 -C 30 alkyl radical having a mean ethoxylation level of 5 to 100 and, among these, particular preference to those having a linear C 12 -C 20 alkyl radical and a mean ethoxylation level of 10 to 50, and also to ethoxylated monoalkylphenols.
  • the surfactants used in the process of the present invention comprise less than 20%by weight, especially not more than 10%by weight, of nonionic surfactants, based on the total amount of surfactants used in the process of the present invention, and especially do not comprise any nonionic surfactant.
  • the surfactants used in the process of the present invention comprise at least one anionic surfactant and at least one non-ionic surfactant, the ratio of anionic surfactants to non-ionic surfactants being usually in the range form 0.5: 1 to 10: 1, in particular from 1: 1 to 5: 1.
  • the surfactant will be used in such an amount that the amount of surfactant is in the range from 0.2 to 5%by weight, especially in the range from 0.5 to 3%by weight, based on the monomers M to be polymerized.
  • the aqueous reaction medium in polymerization may in principle also comprise minor amounts (usually at most 5%by weight) of water-soluble organic solvents, for example methanol, ethanol, isopropanol, butanols, pentanols, but also acetone, etc.
  • water-soluble organic solvents for example methanol, ethanol, isopropanol, butanols, pentanols, but also acetone, etc.
  • the process of the invention is conducted in the absence of such solvents.
  • the polymer latex of the carboxylated polymer is for example obtainable by a single stage or by a multistage emulsion polymerization, in particular an aqueous radical emulsion polymerization, of a monomer composition M.
  • multistage in the context of aqueous emulsion polymerization is well understood to mean that the relative concentration of the monomers in the monomer composition M added to the polymerization reaction is altered at least once during the aqueous emulsion polymerization. Such a procedure results in at least two polymer populations of different monomer compositions in the polymer particles of the latex.
  • the monomer composition such that the multistage latex polymer features populations having different glass transition temperatures or a glass transition temperature (T g ) gradient. It may also be possible to change the monomer composition such that the multistage latex polymer features populations having different concentrations of polymerized acidic monomers, such as monomers M2 or a concentration gradient of monomers M2.
  • the type of monomers and/or the relative amounts thereof can be altered continuously or stepwise.
  • the type and relative amounts of monomers M, which are added to the polymerization reaction remains constant. For example, it is possible that the ratio of monomers M1 and M2 increases or decreases during the addition.
  • the concentration of the polymer latex contained in the aqueous binder composition is frequently in the range from 10 to 70%by weight, in particular in the range from 30 to 65%by weight, especially in the range from 40 to 65%by weight, based in on the total weight of the aqueous binder composition.
  • the aqueous binder composition usually consists of the aqueous polymer latex of a film forming carboxylated polymer as described herein and the polyetheramine polyol as described herein and water.
  • the aqueous binder composition optionally contains further components such as for example dispersants, biocides, and defoamers.
  • the present invention also relates to water-borne coating compositions containing the aqueous binder composition as defined herein.
  • Preferred embodiments of the aqueous binder composition contained in the water-borne coating compositions are those mentioned hereinabove.
  • the coating compositions preferably further contain at least one pigment and/or at least one filler.
  • coating compositions, which do not contain a pigment or filler are also part of the invention.
  • Pigments for the purposes of the present invention are virtually insoluble, finely dispersed, organic or preferably inorganic colorants as per the definition in German standard specification DIN 55944.
  • the composition contains at least one inorganic pigment.
  • organic pigments are examples of organic pigments.
  • - monoazo pigments such as C.I. Pigment Brown 25; C.I. Pigment Orange 5, 13, 36 and 67; C.I. Pigment Red 1, 2, 3, 5, 8, 9, 12, 17, 22, 23, 31, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 52: 1, 52: 2, 53, 53: 1, 53: 3, 57: 1, 63, 112, 146, 170, 184, 210, 245 and 251; C.I. Pigment Yellow 1, 3, 73, 74, 65, 97, 151 and 183;
  • - diazo pigments such as C.I. Pigment Orange 16, 34 and 44; C.I. Pigment Red 144, 166, 214 and 242; C.I. Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 and 188;
  • anthanthrone pigments such as C.I. Pigment Red 168 (C.I. Vat Orange 3) ; anthraquinone pigments, such as C.I. Pigment Yellow 147 and 177; C.I. Pigment Violet 31;
  • anthraquinone pigments such as C.I. Pigment Yellow 147 and 177; C.I. Pigment Violet 31;
  • anthrapyrimidine pigments such as C.I. Pigment Yellow 108 (C.I. Vat Yellow 20) ; quinacridone pigments, such as C.I. Pigment Red 122, 202 and 206; C.I. Pigment Violet 19;
  • quinophthalone pigments such as C.I. Pigment Yellow 138;
  • C.I. Pigment Yellow 24 C.I. Vat Yellow 1
  • C.I. Vat Yellow 1 C.I. Pigment Yellow 24 (C.I. Vat Yellow 1)
  • C.I. Pigment Blue 60 C.I. Vat Blue 4
  • 64 C.I. Vat Blue 6
  • - isoindoline pigments such as C.I. Pigment Orange 69; C.I. Pigment Red 260; C.I. Pigment Yellow 139 and 185;
  • - isoindolinone pigments such as C.I. Pigment Orange 61; C.I. Pigment Red 257 and 260; C.I. Pigment Yellow 109, 110, 173 and 185;
  • C.I. Pigment Orange 43 C.I. Vat Orange 7
  • C.I. Pigment Red 194 C.I. Vat Red 15
  • C.I. Pigment Black 31 and 32 such as C.I. Pigment Black 31 and 32; C.I. Pigment Red 123, 149, 178, 179 (C.I. Vat Red 23) , 190 (C.I. Vat Red 29) and 224; C.I. Pigment Violet 29;
  • - phthalocyanine pigments such as C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and 16; C.I. Pigment Green 7 and 36;
  • C.I. Pigment Orange 51 C.I. Pigment Red 216 (C.I. Vat Orange 4) ;
  • C.I. Pigment Red 88 and 181 C.I. Vat Red 1
  • C.I. Pigment Violet 38 C.I. Vat Violet 3
  • C.I. Pigment Blue 1, 61 and 62 such as C.I. Pigment Blue 1, 61 and 62; C.I. Pigment Green 1; C.I. Pigment Red 81, 81: 1 and 169; C.I. Pigment Violet 1, 2, 3 and 27; C.I. Pigment Black 1 (aniline black) ;
  • preferred organic pigments are C.I. Pigment Yellow 138, C.I. Pigment Red 122, C.I. Pigment Violet 19, C.I. Pigment Blue 15: 3 and 15: 4, C.I. Pigment Black 7, C.I. Pigment Orange 5, 38 and 43, and C.I. Pigment Green 7.
  • white pigments such as titanium dioxide (C.I. Pigment White 6) , zinc white, pigment grade zinc oxide; zinc sulfide, lithopone; lead white; furthermore white fillers such as barium sulfate and CaCO 3 which are also referred to as inorganic white pigments in the context of the present invention
  • iron oxide black C.I. Pigment Black 11
  • iron manganese black C.I. Pigment Black 27
  • carbon black C.I. Pigment Black 7
  • - color pigments such as chromium oxide, chromium oxide hydrate green; chrome green (C.I. Pigment Green 48) ; cobalt green (C.I. Pigment Green 50) ; ultramarine green; cobalt blue (C.I. Pigment Blue 28 und 36) ; ultramarine blue, iron blue (C.I. Pigment Blue 27) , manganese blue, ultramarine violet, cobalt violet, manganese violet, iron oxide read (C.I. Pigment Red 101) ; cadmium sulfoselenide (C.I. Pigment Red 108) ; molybdate red (C.I. Pigment Red 104) ; ultramarine red;
  • Interference pigments such as metallic effect pigments based on coated metal platelets, pearl luster pigments based on mica platelets coated with metal oxide, and liquid crystal pigments.
  • Preferred inorganic pigments are selected from inorganic yellow pigments and inorganic white pigments, especially titanium dioxide, barium sulfate, and CaCO 3 .
  • compositions can also comprise mixtures of two or more different pigments, in which case it is preferable that at least one pigment be inorganic.
  • the pigments are usually in particulate form, i.e., in the form of particles.
  • Pigments can be selected from crude pigments, i. e., untreated as- synthesized pigments.
  • the particles of pigment may be regular or irregular in shape in that, for example, the particles may have a spherical or substantially spherical shape or a needle (acicular) shape.
  • the pigment is in spherical or substantially spherical shape, i. e., the ratio of the longest diameter to the smallest diameter is in the range from 1.0 to 2.0, preferably up to 1.5.
  • the pigment has an average particle diameter (median, d50) in the range of from 20 to 50 pm, measured, e.g., by Coulter counter or with a Hegman gauge.
  • suitable fillers are aluminosilicates, such as feldspars, silicates, such as kaolin, talc, mica, magnesite, alkaline earth metal carbonates, such as calcium carbonate, for example in the form of calcite or chalk, magnesium carbonate, dolomite, alkaline earth metal sulfates, such as calcium sulfate, silicon dioxide, etc.
  • aluminosilicates such as feldspars, silicates, such as kaolin, talc, mica, magnesite, alkaline earth metal carbonates, such as calcium carbonate, for example in the form of calcite or chalk, magnesium carbonate, dolomite, alkaline earth metal sulfates, such as calcium sulfate, silicon dioxide, etc.
  • finely divided fillers are naturally preferred.
  • the fillers may be used in the form of individual components. In practice, however, filler mixtures have been found to be particularly useful, for example calcium carbonate/kaolin, calcium
  • Gloss paints generally comprise only small amounts of very finely divided fillers, or do not comprise any fillers. Fillers also include flatting agents which significantly impair the gloss as desired. Flatting agents are generally transparent and may be either organic or inorganic. Examples of flatting agents are inorganic silicates, for example the brands from W.R. Grace &Company and the brands from Evonik GmbH. Organic flatting agents are obtainable, for example, from BYK-Chemie GmbH under the brands and the brands, and from Deuteron GmbH under the Deuteron brand.
  • the proportion of the pigments and fillers in coating compositions can be described in a manner known per se via the pigment volume concentration (PVC) .
  • compositions usually have a pigment volume concentration (PVC) of at least 5, especially at least 10.
  • PVC pigment volume concentration
  • the PVC will not exceed a value of 60, especially 40, and is specifically in the range from 5 to 60 or 5 to 40.
  • inventive effects of the polymer dispersions are also manifested in varnishes which typically have a pigment/filler content below 5 %by weight, based on the varnish, and correspondingly have a PVC below 5.
  • the water-borne coating compositions of the invention may also comprise customary auxiliaries.
  • the customary auxiliaries will depend on the kind of the coating in a well-known manner and include but are not limited to:
  • Suitable rheology modifying agents include associative thickener polymers and non-associative rheology modifiers.
  • Suitable associative thickener polymers include anionic associate thickeners such as hydrophobically modified acrylate thickeners, also termed HASE thickeners, and nonionic associative thickeners, also termed NiSAT type associative thickeners, including the hydrophobically modified polyethylene oxide urethane rheology modifiers, also termed HEUR or PUR thickeners, and hydrophobically modified polyethyleneoxides, which are also termed HMPE.
  • Suitable non-associative rheology modifiers are in particular cellulose based thickeners, especially hydroxyethyl cellulose, but also thickeners based on acrylate emulsions (ASE) . Preference is given to non-associative cellulose based thickeners.
  • the amount of the thickener polymer will depend on the desired viscosity profile and is frequently in the range from 0.05 to 2.5%by weight, in particular 0.1 to 2%by weight of thickener, and especially 0.15 to 1.5%by weight, based on the latex paint.
  • Suitable wetting agents or dispersants are, for example, sodium polyphosphates, potassium polyphosphates or ammonium polyphosphates, alkali metal salts and ammonium salts of acrylic acid copolymers or maleic anhydride copolymers, polyphosphonates, such as sodium 1-hydroxyethane-1, 1-diphosphonate, and naphthalenesulfonic salts, especially the sodium salts thereof.
  • Suitable filming auxiliaries are solvents and plasticizers.
  • Plasticizers in contrast to solvents, have a Iow volatility and preferably have a boiling point at 1013 mbar of higher than 250°C while solvents have a higher volatility than plasticizers and preferably have a boiling point at 1013 mbar of less than 250°C.
  • Suitable filming auxiliaries are, for example, white spirit, pine oil, propylene glycol, ethylene glycol, butyl glycol, butyl glycol acetate, butyl glycol diacetate, butyl diglycol, butylcarbitol, 1-methoxy-2-propanol, 2, 2, 2-trimethyl-1, 3-pentanediol monoisobutyrate and the glycol ethers and esters, commercially available, for example, from BASF SE under the and names, and from Dow under the trade name.
  • the amount is preferably ⁇ 10%by weight and more preferably ⁇ 5%by weight, based on the overall formulation. Formulation is also possible completely without solvents.
  • a further embodiment of the present invention are methods of producing a coating on a surface comprising
  • the composition can be applied to surfaces and/or substrates to be coated in a customary manner such as for example by applying the paint with brushes or rolls, by spraying, by dipping, by rolling, or by bar coating.
  • the coating of surfaces and/or substrates is effected in such a way that the surface and/or substrate is first coated with a composition of the invention and then the aqueous composition is subjected to a drying step.
  • the composition can be applied to surfaces such as for example metal, asphalt, concrete, fiber boards, stone, ceramic, minerals, wood, plastic, polymer, and glass.
  • the composition can be applied to interior or exterior surfaces such as for example an architectural surface such as a roof, a wall, a floor, and a ceiling.
  • the composition can be applied to exterior surfaces.
  • An aqueous binder composition comprising
  • carboxylated polymer is obtainable by a radical emulsion polymerization of a monomer composition M using a reduction-oxidation initiator system, where the monomer composition M comprises:
  • ethylenically unsaturated monomers M1 which are selected from C 1 -C 20 -alkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, di-C 1 -C 20 -alkyl esters of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, C 5 -C 20 -cycloalkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, vinylesters of C 1 -C 20 -alkanoic acids, vinyl aromatic monomers, C 2 -C 6 -monoolefines and conjugated dienes; and
  • ethylenically unsaturated monomers M2 which are selected from ethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms and ethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms.
  • polyetheramine polyol has a weight-average molecular weight M w in the range of 1000 to 300000 g/mol, in particular in the range from 2000 to 200000 g/mol, and especially in the range from 5000 to 150000 g/mol.
  • At least one monomer M1a selected from C 1 -C 20 -alkyl esters of acrylic acid, C 5 -C 20 -alkylesters of methacrylic acid and mixtures thereof; and
  • At least one monomer M1b selected from vinyl aromatic monomers, C 1 -C 4 -alkyl esters of methacrylic acid and mixtures thereof.
  • aqueous binder composition according to any one of embodiments 1 to 11 as a binder or co-binder in a water-borne coating composition.
  • NaPS Sodium persulfate
  • TAHP tert-amyl hydroperoxide
  • Disponil FES 27 an emulsifier from BASF
  • Seed 6772 an aqueous polystyrene seed dispersion, solid content of 33 wt%, from BASF Advanced Chemicals Co. Ltd.
  • Baxxdour EC302 Polyethyleneimine, 100 wt%in water, from BASF,
  • Lupasol SC61 Polyetheramine polyol (>20% tertiary amine groups, 100000 ⁇ 150000 M w average) , 37 wt%in water, from BASF
  • the solids content was determined by drying a defined amount of the aqueous polymer dispersion (about 2 g) to constant weight in an aluminum crucible having an internal diameter of about 5 cm at 120°C in a drying cabinet (about 2 hours) . Two separate measurements were conducted. The value reported in the example is the mean of the two measurements.
  • the particle diameter of the polymer latex was determined by dynamic light scattering of an aqueous polymer dispersion diluted with deionized water to 0.001 to 0.5%by weight at 22°C by means of a High Performance Particle Sizer (HPPS) from Malvern Instruments, England. What is reported is the cumulant Z average diameter calculated from the measured autocorrelation function (ISO Standard 13321) .
  • the glass transition temperature was determined by the DSC method (Differential Scanning Calorimetry, 20 K/min, midpoint measurement, DIN 53765: 1994-03) by means of a DSC instrument (Q 2000 series from TA instruments) .
  • the molecular weight was determined by GPC using a refractometer as the detector.
  • the mobile phase used was hexafluoroisopropanol (HFIP) , the standard employed for determining the molecular weight being polymethylmethacrylate (PMMA) .
  • HFIP hexafluoroisopropanol
  • the OH number of the polyether amine polyol was determined in accordance with DIN 53240, part 2.
  • the dynamic viscosity of the polyetheramine polyol was determined at 23°C and a shear rate of 100 sec -1 according to ASTM D7042.
  • the amine number was determined by a standard protocol according to DIN EN ISO 9702: 1998.
  • the early rain resistance test was carried out by spreading a paint film with a thickness of 100 ⁇ m on black leneta paper, curing under 5°C/90%RH condition for 20 minutes, then rinsing by waterflow with different flowrate for 5 minutes, wherein “Small rain” represents waterflow of 400g/min and “Heavy rain” represents waterflow of 7000g/min. “PASS” represents no film break found after waterflow rinsing. “FAIL” represents film had break after waterflow rinsing.
  • Example 1 to 16 preparation of an aqueous binder composition
  • DI water 195.9g, Seed 6772 35.8g was loaded into a reactor and the reactor was heated up to 60°C. During heating, DI water 167.6g, Disponil FES27 33.7g, AA 10.10g, styrene 226.1g and nBA 235.9g were all mixed together as a pre-emulsion.
  • the reactor temperature was stable at 60°C, 10%TBHP 7.2g, 5%Dissolvine E-FE-13 1.5g and 1%SFS 7.2g were shotted into the reactor one by one. After 10 minutes, the pre-emulsion was fed for 150 minutes and 1%SFS 21.2g was fed for 165 minutes simultaneously, and post polymerization was performed for 15 minutes after completing feeding SFS.
  • Example 2 was carried out in the same manner as Example 1, with the exception that the reactor temperature was 50°C, instead of 60°C.
  • Example 3 was carried out in the same manner as Example 1, with the exception that the reactor temperature was 40°C, instead of 60°C.
  • Example 4 was carried out in the same manner as Example 1, with the exception that SAB was used in place of SFS.
  • Example 5 was carried out in the same manner as Example 1, with the exception that TAHP was used in place of TBHP.
  • DI water 195.9g, Seed 6772 35.8g was loaded into a reactor and the reactor was heated up to 60°C. During heating, DI water 167.6g, Disponil FES27 33.7g, AA 10.10g, styrene 226.1g and nBA 235.9g were all mixed together as a pre-emulsion.
  • the reactor temperature was stable at 60°C, 53%TBHP 7.2g, 5%Dissolvine E-FE-13 1.5g and 5%SFS 7.2g were shotted into the reactor one by one. After 10 minutes, the pre-emulsion was fed for 150 minutes and 5%SFS 21.2g was fed for 165 minutes simultaneously, and post polymerization was performed for 15 minutes after completing feeding SFS.
  • Example 7 was carried out in the same manner as Example 1, with the exception that 30g Polystar 25 was used.
  • Example 8 was carried out in the same manner as Example 1, with the exception that Lupasol SC61 was used in place of Polystar 25.
  • DI water 195.9g, Seed 6772 35.8g was loaded into a reactor and the reactor was heated up to 60°C. During heating, DI water 167.6g, Disponil FES27 33.7g, AA 10.10g, styrene 226.1g and nBA 235.9g were all mixed together as a pre-emulsion.
  • the reactor temperature was stable at 60°C, 53%TBHP 18g, 5%Dissolvine E-FE-13 1.5g and 10%SFS 12g were shotted into the reactor one by one. After 10 minutes, the pre-emulsion was fed for 150 minutes and 10%SFS 36g was fed for 165 minutes simultaneously, and post polymerization was performed for 15 minutes after completing feeding SFS.
  • This example is a comparative example.
  • DI water 195.9g, Seed 6772 35.8g was loaded into a reactor and the reactor was heated up to 60°C. During heating, DI water 167.6g, Disponil FES27 33.7g, AA 10.10g, styrene 226.1g and nBA 235.9g were all mixed together as a pre-emulsion.
  • 10%TBHP 4.8g, 5%Dissolvine E-FE-13 1.5g and 0.1%SFS 1.2g were shotted into the reactor one by one. After 10 minutes, the pre-emulsion was fed for 150 minutes and 0.1%SFS 3.5g was fed for 165 minutes simultaneously. The polymerization cannot be started since there is no exothermal phenomenon. Therefore, dispersion could not be made successfully.
  • This example is a comparative example.
  • DI water 195.9g, Seed 6772 35.8g was loaded into a reactor and the reactor was heated up to 85°C. During heating, DI water 167.6g, Disponil FES27 33.7g, AA 10.10g, styrene 226.1g and nBA 235.9g were all mixed together as a pre-emulsion.
  • 7%NaPS 6.9g was shotted into the reactor one by one. After 10 minutes, the pre-emulsion was fed for 150 minutes and 7%NaPS 20.2g was fed for 165 minutes simultaneously, and post polymerization was performed for 15 minutes after completing feeding SFS. Then 5.7g ammonia (25%) was added for 20 minutes. After neutralization, 10%TBHP 7g and 10%SFS 8g were fed for 60 minutes simultaneously. However, the dispersion was found with too much coagulum, no stable dispersion could be obtained.
  • This example is a comparative example.
  • DI water 195.9g, Seed 6772 35.8g was loaded into a reactor and the reactor was heated up to 85°C. During heating, DI water 167.6g, Disponil FES27 33.7g, AA 10.10g, styrene 226.1g and nBA 235.9g were all mixed together as a pre-emulsion.
  • 7%NaPS 17.3g were shotted into the reactor one by one. After 10 minutes, the pre-emulsion was fed for 150 minutes and 7%NaPS 50.5g was fed for 165 minutes simultaneously, and post polymerization was performed for 15 minutes after completing feeding SFS. Then 5.7g ammonia (25%) was added for 20 minutes.
  • This example is a comparative example.
  • Example 14 was carried out in the same manner as Example 13, with the exception that no Polystar 25 was used.
  • This example is a comparative example.
  • Example 15 was carried out in the same manner as Example 1, with the exception that Baxxdour EC302 was used in place of Polystar 25.
  • This example is a comparative example.
  • Example 16 was carried out in the same manner as Example 1, with the exception that triethanolamine (TEA) was used in place of Polystar 25.
  • TAA triethanolamine
  • This example is a comparative example.
  • the percentage of oxidizing agent and reducing agent and polyetheramine polyol/polyethyleneimine/triethanolamine used in the water-borne coating composition of each Example are shown in Table 1 below. Further, the results of Early Rain Resistance (ERR) and tensile properties of the water-borne coating composition are shown in Table 1 below.
  • ERP Early Rain Resistance
  • the inventive coating samples can withstand washing by rain and show good tensile properties.
  • the comparative coating samples cannot withstand washing by heavy rain, even though the comparative coating samples of Examples 10 and 13 can withstand washing by small rain.
  • the elongation at break and tensile strength of the comparative coating samples of Examples 10 and 13 are much lower than the inventive coating samples.

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Abstract

The present invention relates to aqueous binder compositions comprising an aqueous polymer latex of a carboxylated polymer and a polyetheramine polyol dissolved in the aqueous polymer latex, wherein at least 20wt%of the amino groups among all the amino groups in the polyetheramine polyol are tertiary amine groups and wherein the carboxylated polymer is obtainable by a radical emulsion polymerization of a monomer composition via a redox initiator system. The present invention also relates to water-borne coating compositions containing such an aqueous binder composition. The present invention further relates to the use of the aqueous binder composition as a binder or co-binder in a water-borne coating composition.

Description

Aqueous Binder Compositions and Water-borne Coating Compositions Comprising the Same Technical Field
The present invention relates to aqueous binder compositions comprising an aqueous polymer latex of a carboxylated polymer and a polyetheramine polyol. The present invention also relates to water-borne coating compositions containing an aqueous binder composition according to the present invention.
Background
Application of a water-borne coating, in particular for outdoor use such as a wood coating, is highly dependent on the weather conditions. For example, rainfall during and/or after coating applications may wash-off some or all of the coating, resulting in coating failure.
By shortening the setting time of coatings, instances of coating failure, such as those due to unanticipated rainfall, can be minimized. Towards this end, some additives have been incorporated into coatings to decrease the setting time of coatings. For example, some additives based on water soluble polymeric amines or imines are incorporated into coatings to decrease the setting time of coatings in a certain degree. However, coatings containing these additives may be still washed off by rain, in particular heavy rain, when applied at low temperatures and high atmospheric humidity. Furthermore, coatings containing these additives suffer from serious drawbacks, including decreased tensile properties and significant yellowing upon weathering. As a result, these coatings have proved unsuitable for many applications, in particular at low temperatures and high atmospheric humidity when suffering rainfall, especially heavy rain after newly coated.
WO 2014/060456 describes aqueous coating compositions containing an anionically stabilized polymer latex and one or more derivatized polyamines, which contain a plurality of primary amine groups, secondary amine groups or combinations thereof and which are in particular alkoxylated polyethylene imines, together with a volatile base. The derivatized polyamine decreases the setting time of the coating compositions. However, the drying speed of the coating at higher temperature is too rapid and the open time is too short.
WO 2019/145265 describes aqueous binder compositions comprising an aqueous polymer latex and a branched polyetheramine polyol. The polymerization was initiated by sodium persulfate (NaPS) initiator which required higher polymerization temperature.
It is known that reduction-oxidation (redox) initiated polymerization can be conducted in a lower temperature. But it is not known in the art how to select suitable amount and ratio of redox initiators for use in the polymerization of aqueous polymer latex to prepare a binder composition with improved physical properties.
Therefore, there is still a need for an aqueous binder composition which can be polymerized in a lower temperature to ensure that the water-borne coating composition comprising the aqueous binder composition can be applied at low temperatures and high atmospheric humidity,  which can prevent to be washed off by rain, in particular heavy rain after coated and at the same time has good physical properties.
Summary description
The object of the present invention is to provide an aqueous binder composition which can be polymerized in a lower temperature, and the water-borne coating composition comprising the aqueous binder composition can prevent to be washed off by rain, in particular heavy rain after coated and at the same time has good tensile properties, even when applied at low temperatures and high atmospheric humidity.
It has been surprisingly found that the object is achieved by an aqueous binder composition comprising an aqueous polymer latex of a carboxylated polymer and a polyetheramine polyol dissolved in the aqueous phase of the aqueous polymer latex, wherein at least 20wt%of the amino groups among all the amino groups in the polyetheramine polyol are tertiary amine groups and wherein the carboxylated polymer is obtainable by a radical emulsion polymerization of a monomer composition via a redox initiator system. It was in particular found that a water-borne coating composition comprising the aqueous binder composition according to the invention can prevent to be washed off by rain, in particular heavy rain after coated and at the same time has good tensile properties, when applied at low temperatures such as 5℃ and high atmospheric humidity such as relative humidity (RH) of 90%.
Consequently, a first aspect of the present invention relates to an aqueous binder composition comprising
(a) an aqueous polymer latex of a carboxylated polymer;
(b) a polyetheramine polyol dissolved in the polymer latex, wherein at least 20wt%of the amino groups among all the amino groups in the polyetheramine polyol are tertiary amine groups;
wherein the carboxylated polymer is obtainable by a radical emulsion polymerization of a monomer composition M via a redox initiator system, where the monomer composition M comprises:
i) 70%by weight to 99.95%by weight, based on the total weight of the monomer composition M, of one or more ethylenically unsaturated monomers M1, which are selected from C1-C20-alkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, di-C1-C20-alkyl esters of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, C5-C20-cycloalkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, vinylesters of C1-C20-alkanoic acids, vinyl aromatic monomers, C2-C6-monoolefines and conjugated dienes; and
ii) 0.05%by weight to 30%by weight, based on the total weight of the monomer composition M, of one or more ethylenically unsaturated monomers M2, which are selected from ethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms and ethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms,
A second aspect of the present invention relates to a water-borne coating composition containing the aqueous binder composition as defined herein.
A third aspect of the present invention relates to the use of an aqueous binder composition as defined herein as a binder or co-binder in the water-borne coating compositions.
A further aspect of the present invention relates to a method of producing a coating on a surface comprising applying the aqueous binder composition as described herein and/or the water-borne coating composition as described herein to the surface, and allowing the compositions to dry to produce the coating.
Detailed description
The present invention will be described in detail hereinafter. It is to be understood that the present invention can be embodied in many different ways and shall not be construed as limited to the embodiments set forth herein.
Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by a person skilled in the art to which the invention belongs. As used herein, the following terms have the meanings ascribed to them below, unless specified otherwise.
As used herein, the articles “a” and “an” refer to one or to more than one (i.e., to at least one) of the grammatical object of the article or component.
As used herein, the terms “comprise” , “comprising” , etc. are used interchangeably with “contain” , “containing” , etc. and are to be interpreted in a non-limiting, open manner. That is, e.g., further components or elements can be present. The expressions “consists of” or “consists essentially of” or cognates can be embraced within “comprises” or cognates.
Unless otherwise identified, all percentages (%) are “percent by weight (wt%) ” and parts indicate parts by weight.
Here and throughout the specification, the prefixes Cn-Cm used in connection with compounds or molecular moieties each indicate a range for the number of possible carbon atoms that a molecular moiety or a compound can have. The term “C1-Cn alkyl” denominates a group of linear or branched saturated hydrocarbon radicals having from 1 to n carbon atoms. For example, the term C1-C20 alkyl denominates a group of linear or branched saturated hydrocarbon radicals having from 1 to 20 carbon atoms. Similarly, term C5-C20 alkyl denominates a group of linear or branched saturated hydrocarbon radicals having from 5 to 20 carbon atoms, while the term C1-C4 alkyl denominates a group of linear or branched saturated hydrocarbon radicals having from 1 to 4 carbon atoms. Examples of alkyl include but are not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, 2-methylpropyl (isobutyl) , 1, 1-dimethylethyl (tert-butyl) , pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2, 2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl and their isomers. C1-C4-alkyl means for example methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1 , 1-dimethylethyl.
Here and throughout the specification, the term “ (meth) acryl” includes both acryl and methacryl groups. Hence the term “ (meth) acrylate” includes acrylate and methacrylate.
Here and throughout the specification, the term “polymer latex” and “polymer dispersion” are used as synonyms and means an aqueous polymer composition of a water-insoluble polymer, where the polymer is present in the form of finely dispersed polymer particles. Usually, the polymer latex is obtainable by emulsion polymerization (also termed primary latex) but it may also be obtainable by emulsifying a polymer in an aqueous phase (secondary latex) .
Here and throughout the specification, the term “polyetheramine polyol” means a polymer having amine groups, ether groups and hydroxyl groups.
Here and throughout the specification, the term “pphm” is the abbreviation for “parts per hundred monomers” and is the weight fraction, based on the total weight of monomers in the respective composition.
Here and throughout the specification, the range “x to y %by weight” is a synonym of the range “x %by weight to y %by weight” . Likewise, the range “x to y mol%” is a synonym of the range “x mol%to y mol% “. For avoidance of any doubt, it is emphasized that the same applies for ranges given in “mol/kg” , “mg KOH/g” , “g/mol” , “pphm” , “℃” and the like.
According to the invention, the binder composition contains an aqueous polymer latex of a carboxylated polymer and a polyetheramine polyol. The polyetheramine polyol is dissolved in the aqueous phase of the polymer latex. Hence, the polyetheramine polyol is water soluble to at least a certain extent.
The water solubility of the polyetheramine polyol is preferably at least 5 g/l, more preferably at least 10 g/l, in particular at least 50 g/l, especially 100 g/l, at 20℃.
In particular, the polyetheramine polyol is completely water miscible at 20℃.
Preferably, the polyetheramine polyol is a branched polyetheramine polyol.
The term “branched” describes that the polyetheramine polyol does not have linear structure, but has a significant amount of branching points within the polymer backbone, which result in a branched polymer chain. Such branching points may be tri or tetra-substituted carbon atoms and/or tertiary amino groups. The branching points are in particular the tertiary amino groups.
In the polyetheramine polyol, which is dissolved in the aqueous phase of the polymer latex, at least 30 wt%of the amino groups are tertiary amine groups, for example at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 60 wt%, at least 70 wt%, at least 90 wt%, at least 95wt %, at least 98 wt%, or at least 99 wt%of the amino groups in the polyetheramine polyol are tertiary amine groups. Especially, the polyetheramine polyol does not have any detectable amounts of secondary and primary amino groups. Thus, in the polyetheramine polyol dissolved in the aqueous phase of the polymer latex, all of the amino groups in the polyetheramine polyol are tertiary amine groups. Frequently, the polyetheramine polyol contains on average less than 0.5 mol/kg of secondary and primary amino groups, if any. In particular, the polyetheramine polyol contains on average less than 0.2 mol/kg, especially less than 0.1 mol/kg of secondary and primary amino groups, if any.
Frequently, the polyetheramine polyol contains on average from 1 to 8.2 mol/kg of tertiary amino groups. In particular, the polyetheramine polyol contains on average from 2 to 8.0 mol/kg of tertiary amino groups, especially from 4 to 7.9 mol/kg.
The amine number of polyetheramine polyol is preferably in the range of 100 to 700 mg KOH/g, more preferably in the range of 200 to 500 mg KOH/g, determined according to the method described in DIN EN ISO 9702: 1998. Besides determination of the total amine group content, this method allows for determination of the tertiary amine group content, the secondary amine group content, and the primary amine group content.
In addition to the amino groups, the polyetheramine polyol may contain hydroxyl groups. The OH number of the polyetheramine polyol is frequently at least 100 mg KOH/g, e.g., 100 to 800 mg KOH/g, in particular at least 200 mg KOH/g, e.g., 200 to 700 mg KOH/g, especially at least 250 mg KOH/g, e.g., 250 to 650 mg KOH/g, determined according to DIN 53240, part 2. The number of hydroxyl groups per molecule will depend on the number average molecular weight of the polyetheramine polyol and the degree of branching. Frequently, the polyetheramine polyol contains on average (number average) at least four, more preferably at least six, more preferably at least ten, hydroxyl groups per molecule. In principle, there is no upper limit on the number of terminal or pendent hydroxyl functional groups. Preferably, the polyetheramine polyol contains on average (number average) at most 500, in particular at most 200 terminal hydroxyl groups per molecule.
The weight-average molecular weight, Mw, of the polyetheramine polyol is frequently in the range of from 1000 to 300000 g/mol, in particular in the range from 2000 to 200000 g/mol, and especially in the range from 5000 to 150000 g/mol, , such as 5000 g/mol, 10000 g/mol, 20000 g/mol, 30000 g/mol, 40000 g/mol, 50000 g/mol, 60000 g/mol, 70000 g/mol, 80000 g/mol, 90000 g/mol, 100000 g/mol, 120000 g/mol, 140000 g/mol, 160000 g/mol, 180000 g/mol, 200000 g/mol, 220000 g/mol, 240000 g/mol, 260000 g/mol, 280000 g/mol, determined by gel permeation chromatography using hexafluoroisopropanol as the mobile phase and polymethylmethacrylate as a standard. The number average molecular weight, Mn, of the polyetheramine polyol is frequently in the range of from 500 to 155000 g/mol, in particular in the range from 1000 to 60000 g/mol, such as 5000 g/mol, 10000 g/mol, 20000 g/mol, 30000 g/mol, 40000 g/mol, 50000 g/mol, 60000 g/mol, 70000 g/mol, 80000 g/mol, 90000 g/mol, 100000 g/mol, 110000 g/mol, 120000 g/mol, 130000 g/mol, 140000 g/mol, 150000 g/mol, determined by gel permeation chromatography using hexafluoroisopropanol as the mobile phase and polymethylmethacrylate as a standard. The polydispersity, i.e., the ratio Mw/Mn, of the polyetheramine polyol is frequently in the range of from 1.1 to 25, in particular in the range of 1.5 to 20, such as 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, etc.
The dynamic viscosity of the polyetheramine polyol is frequently in the range of from 5 to 200 Pa·s, determined at 23℃ according to ASTM D7042, in particular in the range from 8 to 150 Pa·s.
The Hazen color number of the polyetheramine polyol is preferably in the range of from 100 to 600 (APHA) , determined according to DIN ISO 6271.
The polyetheramine polyol is frequently amorphous and thus may show a glass transition. Preferably, the glass transition temperature of the polyetheramine polyol does not exceed 50℃, more preferably, it does not exceed 30℃ and more preferably not exceed 10℃, determined by differential scanning calorimetry (DSC) , as described below. The glass transition temperature of the polyetheramine polyol is preferably in the range of-55 to 30℃ and more preferably in the range of-55 to 10℃, determined by DSC. Polyetheramine polyols and their preparation are known, for example from DE 3206459, EP 441 198, WO 2009/047269, WO 2014/012812, which  disclose polyetheramine polyols based on a polycondensation product of at least one trialkanolamine.
In one embodiment of the present invention, the polyetheramine polyol is obtainable by polycondensation of at least one trialkanolamine or by polycondensation of a mixture of at least one trialkanolamine with an aliphatic or cycloaliphatic polyol. For this purpose, trialkanolamines are preferably selected from tri-C2-C8-alkanol amines, wherein the alkanol groups in trialkanolamine may be different or identical, wherein the alkanol groups are preferably identical. More preferably, the trialkanolamines are selected from tri-C2-C4-alkanol amines, wherein the alkanol groups are identical.
Particularly preferred trialkanolamines are triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, and triisobutanolamine and mixtures thereof.
Suitable aliphatic or cycloaliphatic polyols are for example aliphatic diols, aliphatic polyols bearing more than 2 hydroxyl groups, cycloaliphatic diols, and cycloaliphatic polyols having more than 2 hydroxyl groups. Preferred are aliphatic diols and aliphatic polyols bearing more than 2 hydroxyl groups. Examples of aliphatic diols are C2-C20-diols, such as ethandiol, propandiol, butandiol, pentandiol, hexandiol, heptandiol, octandiol, and their structural isomers. Further examples of aliphatic diols are polyether diols of the general formula HO- ( (CH2) n-O) m-H with n being independently from each other 1 to 10, preferably 2 to 4 and m being in the range of 2 to 100. Preferably, the polyether diols are selected from polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymers thereof. Examples of polyols having more than 2 hydroxyl groups are glycerol, pentaerythritol, trimethylolpropane, sorbitol, and the like. The polyols may also be alkoxylated, in particular ethoxylated or propoxylated, e.g., ethoxylated glycerol, propoxylated glycerol, ethoxylated pentaerythritol, propoxylated pentaerythritol, ethoxylated trimethylolpropane, propoxylated trimethylolpropane, ethoxylated sorbitol and propoxylated sorbitol. Usually the degree of alkoxylation, i.e., the number average of alkyleneoxide moieties, will not exceed 100 and is frequently in the range from 2 to 50.
Preferably, the polyetheramine polyol is obtainable by polycondensation, wherein monomers contain to at least 50%by weight, preferably at least 70%by weight, more preferably at least 80%by weight, based on the total amount of monomer, of compounds selected from trialkanolamines. The polyetheramine polyol is preferably obtainable by polycondensation of monomers containing 50 to 100 mol%of compounds selected from trialkanolamines and 0 to 50 mol%of compounds selected from aliphatic or cycloaliphatic polyols, preferably containing 70 to 100 mol%of compounds selected from trialkanolamines and 0 to 30 mol%of compounds selected from aliphatic or cycloaliphatic polyols, more preferably containing 80 to 100 mol%of compounds selected from trialkanolamines and 0 to 20 mol%of compounds selected from aliphatic or cycloaliphatic polyols, whereby “mol%” are based on the total amount of monomers.
In a particular embodiment, the polyetheramine polyol is obtainable by polycondensation, wherein monomers consist only of monomers selected from trialkanolamines. The trialkanolamine is preferably selected from tri-C2-C4-alkanolamines. Preferred tri-C2-C4-alkanolamines are selected from triethanolamine, triisopropanolamine, and tri-n-propanolamine.
The mixture of at least one trialkanolamine with an aliphatic or cycloaliphatic polyol is preferably selected form mixtures of at least one trialkanolamine, which is selected from the group consisting of tri-C2-C4-alkanolamines, and an aliphatic or cycloaliphatic C2-C8-polyol.
Particular preference is given to polyetheramine polyols obtainable by polycondensation of either triethanolamine, or of triisopropanolamine, or of a mixture of triethanolamine and triisopropanolamine. In this embodiment, optionally at least one further polyol, in particular at least one further diol might be present.
The polycondensation can be carried out with or without the presence of a catalyst. Suitable catalysts include but are not limited to phosphoric acid (H3PO4) , phosphorous acid (H3PO3) or hypophosphoric acid (H3PO2) , which can be applied in bulk or as aqueous solution. Preferably, the catalyst is added in an amount of from 0.001 to 10 mol%, preferably from 0.005 to 7 mol%, more preferably from 0.01 to 5 mol%, based on the amount of the trialkanolamine.
The polycondensation can be carried out by using a solvent. Examples of solvents that can be used are aromatic and/or (cyclo) aliphatic hydrocarbons and their mixtures, halogenated hydrocarbons, ketones, esters, and ethers. Preference is given to aromatic hydrocarbons, (cyclo) aliphatic hydrocarbons, alkyl esters of alkanoic acids, ketones, alkoxylated alkyl esters of alkanoic acids, and mixtures thereof. Particularly preferred are monoalkylated or polyalkylated benzenes and naphthalenes, ketones, alkyl esters of alkanoic acids, and alkoxylated alkyl esters of alkanoic acids and mixtures thereof. The polycondensation is preferably carried out without using a solvent.
The polycondensation can be carried out in a way that the temperature during polycondensation does not exceed 250℃ and preferably not exceed 230℃. For example, the polycondensation is carried out at temperatures in the range of from 150 to 230℃, preferably 180 to 215℃. Even more preferably, the temperature during polycondensation does not exceed 215℃ and especially not exceed 210℃.
The polycondensation can be carried out at a pressure in the range of from 0.02 to 20 bar. Preferably, the polycondensation is carried out at normal pressure. The polycondensation is preferably followed by removal or blow-off of residual monomers, for example by distilling them off at normal pressure or at reduced pressure, for example, in the range of from 0.1 to 0.5 bar.
Water or other volatile products that are released during the polycondensation can be removed from the reaction mixture in order to accelerate the reaction. Preferably, water or other volatile products that are released during the polycondensation are removed, such removal being accomplished by distillation, for example, and optionally under reduced pressure. The removal of water or of other low molecular mass reaction by-products can also be assisted by passing through the reaction mixture a stream of gas which is substantially inert under the reaction conditions (stripping) , such as nitrogen, for example, or a noble gas such as helium, neon, or argon, for example.
The polyetheramine polyols described herein are typically stable at room temperature for a prolonged period, such as for at least 10 weeks, for example. In particular, the polyetheramine polyols are stable without exhibiting instances of clouding, precipitation, and/or significant increase in viscosity.
The polycondensation can be terminated by a variety of options. For example, the temperature can be lowered to a range in which the reaction comes to a standstill and the polycondensation product is storage-stable. This is generally the case below 100℃, preferably below 60℃, more preferably below 40℃, and very preferably at room temperature. Another option is to deactivate the catalyst by adding a basic component, a Lewis base or an organic or inorganic base, for example.
The polycondensation can be carried out in stirred tank reactors or stirred tank reactor cascades. The process can be carried out batch-wise, in semi-batch mode or continuously. Polycondensation products of trialkanolamines and poly-co-condensation products of trialkanolamines as described herein are preferably used as polyetheramine polyol without chemical modification or derivatization. However, a derivative of a polycondensation product of trialkanolamines or a derivative of a poly-co-condensation product of a trialkanolamine can be used instead of a non-derivatized polycondensation or poly-co-condensation product.
Derivatives of such polycondensation and poly-co-condensation products of trialkanolamines include products obtained by alkoxylation of the hydroxyl end groups of the non-derivatized polycondensation and poly-co-condensation products. Likewise, it is possible to modify the non-derivatized polycondensation or poly-co-condensation products by hydrophobic groups or hydrophilic groups. Hydrophobization or hydrophilization can be achieved by reacting a part of the hydroxylic end groups with selected reactants. The amino groups of the polycondensation and poly-co-condensation products can also be quaternized to obtain permanently cationic modified polymers by use of alkylating agents. Derivatives of such polycondensation and poly-co-condensation products of trialkanolamines are described for example in US 2011/0168045, WO 2009/060060 and WO 2009/1112379 to which reference is made. For the purpose of the invention, preferred derivatized products are alkoxylated polycondensation and poly-co-condensation products.
The polyetheramine polyol usually dissolves readily in a variety of solvents, such as water, alcohols, such as methanol, ethanol, n-butanol, alcohol/water mixtures, acetone, 2-butanone, ethyl acetate, butyl acetate, methoxypropyl acetate, methoxyethyl acetate, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene carbonate, or propylene carbonate.
The aqueous binder composition usually contains the polyetheramine polyol in the composition in an amount from 0.01 to 10%by weight, in particular from 0.05 to 7.5%by weight, more particular from 0.1 to 5%by weight based on the dry weight of the carboxylated polymer of the aqueous polymer latex.
The aqueous binder composition of the invention also contains an aqueous polymer latex of a carboxylated polymer, also referred as a film forming carboxylated polymer.
The term “film forming” in the context of the polymer latex means the ability of the carboxylated polymer of the polymer latex to form a film on surfaces upon drying under application conditions. The polymer will frequently have a film forming temperature of at most 50℃, in particular at most 30℃. The film forming temperature may be lowered, for example by addition of film forming aids, such as plasticizers and solvents.
The capability of the polymer of the latex to be film forming under application conditions will depend on its glass transition temperature. In general, the carboxylated polymer of the aqueous polymer dispersions has a glass transition temperature Tg in the range from -20 to +60℃, in particular from 0 to +50℃, especially in the range from +5 to +40℃. The glass transition temperature can be determined by the DSC method (differential scanning calorimetry, 20 K/min, midpoint measurement) in accordance to DIN 53765: 1994-03 or ISO 1 1357-2, with sample preparation preferably to DIN EN ISO 16805: 2005.
In case of a multi-phase polymer containing 2 or more polymers or polymer phases, respectively, with different glass transition temperatures, the glass transition temperatures of the  individual polymer phases may be outside the ranges given here. However, the weight average glass transition temperature Tg (av) as calculated by the equation
Tg (av) = (Tg (1) ＊w1+ Tg (2) ＊w2....Tg (n) ＊wn)
is frequently in the range from -20 to +60℃, in particular form 0 to +50℃, especially in the range from +5 to +40℃. In the equation, Tg (1) , Tg (2) to Tg (n) indicate the individual glass transition temperatures in K of the individual polymers 1, 2 to n while w1, w2 to wn indicate the amount in %by weight of the individual polymers 1, 2 to n. If the polymer of the aqueous polymer dispersions contains polymers having different Tg′s, the difference between the lowest Tg and the highest Tg may be as high as e.g., 100℃, e.g. from 10 to 100℃. Preferably, the polymer dispersed in the aqueous polymer dispersion has only one Tg, or, if it contains polymers having different Tg′s, the maximum difference of the lowest Tg and the highest Tg does not exceed 50 K, in particular 20 K.
According to Fox (T. G. Fox, Bull. Am. Phys. Soc. 1956, vol. 1, page 123) and according to Ullmann′s Encyclopadie der technischen Chemie [Ullmann′s Encyclopedia of Industrial Chemistry] (vol. 19, page 18, 4th edition, Verlag Chemie, Weinheim, 1980) , the following is a good approximation of the glass transition temperature of no more than lightly crosslinked copolymers:
1/Tg (Fox) = x1/Tg1 + x2/Tg2 +....xn/Tgn,
where x1, x2, ....xn are the mass fractions of the monomers 1, 2,...., n and Tg1, Tg2,...., Tgn are the glass transition temperatures in degrees Kelvin of the polymers synthesized from only one of the monomers 1, 2,...., n at a time. The Tg values for the homopolymers of most monomers are known and listed, for example, in Ullmann’s Encyclopedia of Industrial Chemistry, 5th ed., vol. A21, page 169, Verlag Chemie, Weinheim, 1992; further sources of glass transition temperatures of homopolymers are, for example, J. Brandrup, E.H. Immergut, Polymer Handbook, 1 st Ed., J. Wiley, New York 1966, 2nd Ed. J. Wiley, New York 1975, and 3rd Ed. J. Wiley, New York 1989.
In case of a multi-stage polymer containing two polymers or polymer phases having different glass transition temperatures, the glass transition temperature of the one phase is usually above 40℃, preferably at least 60℃, determined via DSC as described herein. The glass transition temperature of the other phase, according to Fox, is usually below 40℃, preferably at most 30℃, determined via DSC as described herein.
In case of a multi-stage polymer containing two polymers or polymer phases having different glass transition temperatures, the polymer preferably contains 95 to 40%by weight, based on the total weight of the polymer, of the polymer with the lower glass transition temperature, which is usually below 40℃, and 5 to 60%by weight, based on the total weight of the polymer, of the polymer with the higher glass transition temperature, which is usually above 40℃.
The term “carboxylated polymer” means that the polymer of the latex bears carboxyl groups attached to the polymer backbone. Usually, the carboxyl groups are incorporated into the polymer by means of polymerized ethylenically unsaturated monomers having one or more carboxyl group. Such monomers are typically selected from monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms and monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms. Examples of such monomers are acrylic acid, methacrylic acid, crotonic acid, 2-ethylpropenoic acid, 2-propylpropenoic acid, itaconic acid, and fumaric acid.
The carboxylated polymer of the polymer latex is usually obtainable by a radical copolymerization of a monomers M forming the carboxylated monomer latex. These monomers M, which are also termed monomer composition M, comprise at least one monoethylenically unsaturated monomer having at least one carboxyl group, which is, for example, selected from monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms and monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, and at least one further neutral ethylenically unsaturated monomer, which is essentially water insoluble, i.e. which has a solubility in deionized water of at most 50 g/l at 20℃. Usually, said monomer composition comprises from 0.05 to 10%by weight, based on the total weight of the monomers contained in the monomer composition, of one or more monoethylenically unsaturated monomer having at least one carboxyl group.
The energy consumption (heat) for the carboxylated polymer synthesis is lower. The reaction temperature of the synthesis is generally below 80℃, preferably below 70℃, more preferably at 60℃ or below.
In particular, the monomer composition M essentially consists of
a) one or more ethylenically unsaturated monomers M1, which have a solubility in deionized water of at most 50 g/l at 20℃ and which are in particular selected C1-C20-alkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, di-C1-C20-alkyl esters of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, C5-C20-cycloalkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, vinylesters of C1-C20-alkanoic acids, vinyl aromatic monomers, C2-C6-monoolefines and conjugated dienes;
b) one or more ethylenically unsaturated monomers M2, which are selected from ethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms and ethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms;
c) optionally one or more non-ionic monomers M3, which are different from monomers M1.
In this context, the term “essentially consists of” means that the total amount of monomers M1, M2 and M3 makes up at least 95%by weight, in particular at least 99%by weight or 100%by weight of the total amount of monomers of the monomer composition.
Examples of monomers M1 include, but are not limited to
C1-C20-alkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, such as
- C1-C20-alkyl esters of acrylic acid, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, 2-propylheptyl acrylate, lauryl acrylate, C12/C14-alkyl acrylate, and stearyl acrylate,
-C1-C20-alkylesters of methacrylic acid, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, n-decyl methacrylate, 2-propylheptyl methacrylate, lauryl methacrylate, C12/C14-alkyl methacrylate, and stearyl methacrylate;
-di-C1-C20-alkyl esters of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, such as di-C1-C20-alkyl esters of itaconic acid, di-C1-C20-alkyl esters of citraconic acid, di-C1-C20-alkyl esters of maleic acid and di-C1-C20-alkyl esters of fumaric acid,
-C5-C20-cycloalkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, C5-C20-cycloalkyl esters of acrylic acid and C5-C20-cycloalkyl esters of methacrylic acid,
-vinylesters of C1-C20-alkanoic acids,
-vinyl aromatic monomers such as mono-vinyl substituted aromatic hydrocarbons such as styrene, 2-methylstyrene, 4-methylstyrene, 2-n-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and alpha-methylstyrene,
-C2-C6-monoolefines and conjugated dienes such as butadiene.
In a preferred embodiment, the monomers M1 are a mixture of
- at least one monomer M1a, selected from C1-C20-alkyl esters of acrylic acid, C5-C20-alkylesters of methacrylic acid and mixtures thereof; and
- at least one monomer M1b, selected from vinyl aromatic monomers, C1-C4-alkyl esters of methacrylic acid and mixtures thereof.
Suitable monomers M1a are
- C1-C20-alkyl esters of acrylic acid, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, 2-propylheptyl acrylate, lauryl acrylate, C12/C14-alkyl acrylate, and stearyl acrylate;
- C5-C20-alkylesters of methacrylic acid, such as n-pentyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, n-decyl methacrylate, 2-propylheptyl methacrylate, lauryl methacrylate, C12/C14-alkyl methacrylate, and stearyl methacrylate;
and mixtures thereof.
Suitable monomers M1b are
- C1-C4-alkyl esters of methacrylic acid, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-butyl methacrylate, isobutyl methacrylate and tert. -butyl methacrylate, with particular preference given to methyl methacrylate;
- vinyl aromatic monomers, in particular mono-vinyl substituted aromatic hydrocarbons such as styrene, 2-methylstyrene, 4-methylstyrene, 2-n-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and alpha-methylstyrene, with particular preference given to styrene;
and mixtures thereof.
Preferably, monomers M1a are selected from C2-C10-alkyl esters of acrylic acid, in particular from ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, and 2-propylheptyl acrylate.
Preferably, monomers M1b are selected from vinyl aromatic monomers and C1-C4-alkyl esters of methacrylic acid and mixtures thereof, in particular from styrene, methyl methacrylate.
In the mixtures of monomers M1a and M1b, the relative amount of M1a and M1b may vary in particular from 10∶1 to 1∶10 by weight, more particularly from 5∶1 to 1∶5 by weight, especially from 3∶ 1 to 1∶3 by weight, such as 9∶1, 8∶1, 7∶1, 8∶1, 5∶1, 4∶1, 3∶1, 2∶1, 1∶1, 2∶1, 3∶1, 4∶1, 5∶1, 6∶1, 7∶ 1, 8∶1, 9∶1 by weight, etc.
The amount of M1 used according to the present invention is in the range from 70%by weight to 99.95%by weight, such as 70%by weight, 75%by weight, 80%by weight, 85%by weight, 90%by weight, 95%by weight, 99%by weight, etc., based on the total weight of the monomer composition M.
Examples of monomers M2 include, but are not limited to acrylic acid, methacrylic acid, crotonic acid, 2-ethylpropenoic acid, 2-propylpropenoic acid, itaconic acid and fumaric acid or a mixture thereof. Preferably, monomers M2 is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, 2-ethylpropenoic acid, 2-propylpropenoic acid, itaconic acid and fumaric acid and a mixture thereof. Preference is given to monocarboxylic acids. Particular preference is given to acrylic acid, methacrylic acid, and mixtures thereof.
Especially preferred, the monomer M2 is selected from methacrylic acid or a mixture of acrylic acid and methacrylic acid.
The amount of M2 used according to the present invention is in the range from 0.5%by weight to 10%by weight, such as 1%by weight, 2%by weight, 3%by weight, 4%by weight, 5%by weight, 6%by weight, 7%by weight, 8%by weight, 9%by weight, etc., based on the total weight of the monomer composition M.
Examples of monomers M3 include, but are not limited to
- primary amides of monoethylenically unsaturated monocarboxylic acids having 3 to 8 carbon atoms (monomers M3.1) , such as acrylamide and methacrylamide;
- N-C1-C10 alkyl amides of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms (monomers M3.2) , in particular N-C1-C10 alkyl amides of acrylic acid or methacrylic acid, such as N-methyl acrylamide, N-ethyl acrylamide, N-propyl acrylamide, N-isopropyl acrylamide, N-butyl acrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, N-propyl methacrylamide, N-isopropyl methacrylamide and N-butyl methacrylamide;
- monoethylenically unsaturated monomers bearing urea or keto groups (Monomers M3.3) , such as 2- (2-oxo-imidazolidin-1-yl) ethyl (meth) acrylate, 2-ureido (meth) acrylate, N- [2- (2-oxooxazolidin-3-yl) ethyl] methacrylate, acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, 2- (acetoacetoxy) ethyl methacrylate, diacetoneacrylamide (DAAM) and diacetonemethacrylamide;
- hydroxyalkyl esters of monoethylenically unsaturated C3-C6 monocarboxylic acids (monomers M3.4) , especially hydroxyalkyl esters of acrylic acid and hydroxyalkyl esters of methacrylic acid, also referred to hereinafter as hydroxyalkyl (meth) acrylates, in particular hydroxy-C2-C4-alkylesters of acrylic acid and hydroxy-C2-C4-alkylesters of methacrylic acid, such as 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, etc.
- monoethylenically unsaturated monomers which bear at least one tri-C1-C4-alkoxysilane group (monomers M3.5) , such as vinyl trimethoxysilane, vinyl triethoxysilane,  methacryloxyethyl trimethoxysilane, methacryloxyethyl triethoxysilane, and mixtures thereof. The amount of said monomers M3.5 will frequently be in the range from 0.01 to 1 pphm.
Monomers M3 may also include a small amount of multiethylenically unsaturated monomers (monomers M3.6) , i.e., monomers having at least 2 non-conjugated ethylenically unsaturated double bounds. The amounts of said monomers M3.6 will generally not exceed 1 pphm. Examples of suitable monomers M3.6 include:
- Diesters of monoethylenically unsaturated C3-C6 monocarboxylic acids with saturated aliphatic or cycloaliphatic diols, in particular diesters of acrylic acid or methacrylic acid, such as the diacrylates and the dimethacrylates of ethylene glycol (1, 2-ethanediol) , propylene glycol (1, 2-propanediol) , 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, neopentyl glycol (2, 2-dimethyl-1, 3-propanediol) or 1, 2-cyclohexanediol;
- monoesters of monoethylenically unsaturated C3-C6 monocarboxylic acids with monoethylenically unsaturated aliphatic or cycloaliphatic monohydroxy compounds, such as the acrylates and the methacrylates of vinyl alcohol (ethenol) , allyl alcohol (2 propen-1-ol) , 2-cyclohexen-1-ol or norbornenol; and
- divinyl aromatic compounds, such as 1, 3-divinyl benzene, 1, 4-divinyl benzene;
and mixtures thereof.
In a particular embodiment of the invention, the monomers M do not contain monomers M3.6 or contain no more than 0.1 pphm of monomers M3.6.
Amongst monomers M3, preference is given to hydroxyalkyl esters of acrylic acid and hydroxyalkyl esters of methacrylic acid, in particular to hydroxy-C2-C4-alkylesters of acrylic acid and hydroxy-C2-C4-alkylesters of methacrylic acid, acrylamide, methacrylamide, and to mixtures thereof.
The carboxylated polymer is preferably obtainable by polymerization of a monomer composition M via a redox initiator system, where the monomer composition M essentially consists of
a) 70 to 99.95%by weight, in particular from 80 to 99.9%by weight, especially from 90 to 99.8%by weight, based on the total weight of the monomer composition M, of one or more monoethylenically unsaturated monomers M1 as defined herein,
b) 0.05 to 10 by weight, in particular from 0.1 to 8 %by weight, especially from 0.2 to 5%by z weight, based on the total weight of the monomer composition M, of one or more ethylenically unsaturated monomers M2 as defined herein,
c) 0 to 20%by weight, in particular from 0 to 10%by weight, especially from 0 to 5%by weight, based on the total weight of the monomer composition M, of one or more non-ionic monomers M3 as defined herein, which are different from monomers M1,
The carboxylated polymer is in particular obtainable by a polymerization of a monomer composition M via a redox initiator system, where the monomer composition M consists of
a) one or more ethylenically unsaturated monomers M1, which are selected from the group consisting of at least one monomer M1 a, selected from C1-C20-alkyl esters of acrylic acid, C5-C20-alkylesters of methacrylic acid and mixtures thereof; and at least one monomer M1b,  selected from vinyl aromatic monomers, and C1-C4-alkyl esters of methacrylic acid and mixtures thereof,
b) one or more ethylenically unsaturated monomers M2, which are selected from the group consisting of ethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms and ethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms;
c) optionally one or more non-ionic monomers M3, which are different from monomers M1,
In a preferred embodiment, the film forming carboxylated polymer is obtainable by a polymerization of a monomer composition M via a redox initiator system, where the monomer composition M essentially consists of
a) 70 to 99.95%by weight, in particular from 80 to 99.9%by weight, especially from 90 to 99.8%by weight, based on the total weight of the monomer composition M, of one or more monoethylenically unsaturated monomers M1, which are selected from the group consisting of at least one monomer M1a, selected from C1-C20-alkyl esters of acrylic acid and C5-C20-alkylesters of methacrylic acid; and at least one monomer M1b, selected from vinyl aromatic monomers, and C1-C4-alkyl esters of methacrylic acid and mixtures thereof,
b) 0.05 to 10%by weight, in particular from 0.1 to 8%by weight, especially from 0.2 to 5%by weight, based on the total weight of the monomer composition M, of one or more ethylenically unsaturated monomers M2 as defined herein,
c) 0 to 20%by weight, in particular from 0 to 10%by weight, especially from 0 to 5%by weight, based on the total weight of the monomer composition M, of one or more non-ionic monomers M3 as defined herein, which are different from monomers M1,
In one embodiment of the present invention, an aqueous binder composition comprises
(a) an aqueous polymer latex of a film forming carboxylated polymer;
(b) a polyetheramine polyol dissolved in the aqueous phase of the polymer latex, wherein at least 20wt%of the amino groups among all the amino groups in the polyetheramine polyol are tertiary amine groups;
wherein the carboxylated polymer is obtainable by a radical emulsion polymerization of a monomer composition M via a redox initiator system, where the monomer composition M comprises:
i) 70%by weight to 99.95%by weight, based on the total weight of the monomer composition M, of one or more ethylenically unsaturated monomers M1, which are selected from C1-C20-alkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, di-C1-C20-alkyl esters of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, C5-C20-cycloalkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, vinylesters of C1-C20-alkanoic acids, vinyl aromatic monomers, C2 -C6 -monoolefines and conjugated dienes; and
ii) 0.05%by weight to 30%by weight, based on the total weight of the monomer composition M, of one or more ethylenically unsaturated monomers M2, which are selected from monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms and monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms,
wherein the redox initiator system is present in a total amount in the range from 0.1%by weight to 2.5%by weight, in particular in the range from 0.15%by weight to 2%by weight, more particular in the range from 0.2 %by weight to 1.5%by weight based on the total weight of the monomer composition M, and
wherein the redox initiator system comprises oxidizing agent and reducing agent in a weight ratio in the range from 1: 1 to 10: 1, in particular in the range from 1: 1 to 5: 1, more particular in the range from 1.1: 1 to 3: 1.
In another embodiment of the present invention, an aqueous binder composition comprises
(a) an aqueous polymer latex of a film forming carboxylated polymer;
(b) a polyetheramine polyol dissolved in the aqueous phase of the polymer latex, wherein at least 20wt%of the amino groups among all the amino groups in the polyetheramine polyol are tertiary amine groups;
wherein the carboxylated polymer is obtainable by a radical emulsion polymerization of a monomer composition M via a redox initiator system, where the monomer composition M comprises:
i) 70%by weight to 99.95%by weight, based on the total weight of the monomer composition M, of one or more ethylenically unsaturated monomers M1, which are a mixture of at least one monomer M1a, selected from C1-C20-alkyl esters of acrylic acid, C5-C20-alkylesters of methacrylic acid and mixtures thereof; and at least one monomer M1b, selected from vinyl aromatic monomers, and C1-C4-alkyl esters of methacrylic acid and mixtures thereof; and
ii) 0.05%by weight to 30%by weight, based on the total weight of the monomer composition M, of one or more ethylenically unsaturated monomers M2, which are selected from ethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms,
wherein the redox initiator system is present in a total amount in the range from 0.1%by weight to 2.5%by weight, in particular in the range from 0.15%by weight to 2%by weight, more particular in the range from 0.2 %by weight to 1.5%by weight based on the total weight of the monomer composition M, and
wherein the redox initiator system comprises oxidizing agent and reducing agent in a weight ratio in the range from 1: 1 to 10: 1, in particular in the range from 1: 1 to 5: 1, more particular in the range from 1.1: 1 to 3: 1.
In another embodiment of the present invention, an aqueous binder composition comprises
(a) an aqueous polymer latex of a film forming carboxylated polymer;
(b) a polyetheramine polyol dissolved in the aqueous phase of the polymer latex, wherein at least 20wt%of the amino groups among all the amino groups in the polyetheramine polyol are tertiary amine groups;
wherein the carboxylated polymer is obtainable by a radical emulsion polymerization of a monomer composition M via a redox initiator system, where the monomer composition M comprises:
i) 70%by weight to 99.95%by weight, based on the total weight of the monomer composition M, of one or more ethylenically unsaturated monomers M1, which are a mixture of n-butyl acrylate (nBA) and styrene; and
ii) 0.05%by weight to 30%by weight, based on the total weight of the monomer composition M, of one or more ethylenically unsaturated monomers M2, which are acrylic acid,
wherein the redox initiator system is present in a total amount in the range from 0.1%by weight to 2.5%by weight, in particular in the range from 0.15%by weight to 2%by weight, more particular in the range from 0.2 %by weight to 1.5%by weight based on the total weight of the monomer composition M, and
wherein the redox initiator system comprises oxidizing agent and reducing agent in a weight ratio in the range from 1: 1 to 10: 1, in particular in the range from 1: 1 to 5: 1, more particular in the range from 1.1: 1 to 3: 1.
In another embodiment of the present invention, an aqueous binder composition comprises
(a) an aqueous polymer latex of a film forming carboxylated polymer;
(b) a polyetheramine polyol dissolved in the aqueous phase of the polymer latex, wherein at least 20wt%of the amino groups among all the amino groups in the polyetheramine polyol are tertiary amine groups;
wherein the carboxylated polymer is obtainable by a radical emulsion polymerization of a monomer composition M via a redox initiator system, where the monomer composition M comprises:
i) 70%by weight to 99.95%by weight, based on the total weight of the monomer composition M, of one or more ethylenically unsaturated monomers M1, which are a mixture of nBA and styrene; and
ii) 0.05%by weight to 30%by weight, based on the total weight of the monomer composition M, of one or more ethylenically unsaturated monomers M2, which are acrylic acid,
wherein the redox initiator system is present in a total amount in the range from 0.1%by weight to 2.5%by weight, in particular in the range from 0.15%by weight to 2%by weight, more particular in the range from 0.2 %by weight to 1.5%by weight based on the total weight of the monomer composition M, and
wherein the redox initiator system comprises oxidizing agent and reducing agent in a weight ratio in the range from 1: 1 to 10: 1, in particular in the range from 1: 1 to 5: 1, more particular in the range from 1.1: 1 to 3: 1, and
wherein the redox initiator system is a combination of tert-butyl hydroperoxide (TBHP) and sodium formaldehyde sulfoxylate (SFS) , a combination of tert-Amyl hydroperoxide (TAHP) and sodium formaldehyde sulfoxylate (SFS) or a combination of tert-butyl hydroperoxide (TBHP) and sodium-acetone bisulfite (SAB) .
In the aqueous carboxylated polymer latex, the dispersed polymers are in the form of polymer particles. The polymer particles typically have an average diameter in the range from 50 to 500 nm, in particular in the range from 60 to 400 nm and especially in the range from 80 to 300 nm. The average particle diameter as referred herein relates to the Z average particle diameter as determined by means of photon correlation spectroscopy (PCS) , also known as quasielastic light scattering (QELS) or dynamic light scattering (DLS) . The measurement method is described in the ISO 13321: 1996 standard. The determination can be carried out using an HPPS (High Performance Particle Sizer) . For this purpose, a sample of the aqueous polymer latex will be diluted and the dilution will be analysed. In the context of DLS, the aqueous dilution may have a polymer concentration in the range from 0.001 to 0.5%by weight, depending on the particle size. For most purposes, a proper concentration will be 0.01%by weight. However, higher or lower concentrations may be used to achieve an optimum signal/noise ratio. The dilution can be achieved by addition of the polymer latex to water or an aqueous solution of a  surfactant in order to avoid flocculation. Usually, dilution is performed by using a 0.1%by weight aqueous solution of a non-ionic emulsifier, e.g., an ethoxylated C16/C18 alkanol (degree of ethoxylation of 18) , as a diluent. Measurement configuration: HPPS from Malvern, automated, with continuous-flow cuvette and Gilson autosampler. Parameters: measurement temperature 20.0℃; measurement time 120 seconds (6 cycles each of 20 s) ; scattering angle 173°; laser wavelength 633 nm (HeNe) ; refractive index of medium 1.332 (aqueous) ; viscosity 0.9546 mPa-s. The measurement gives an average value of the second order cumulant analysis (mean of fits) , i.e., Z average. The “mean of fits” is an average, intensity-weighted hydrodynamic particle diameter in nm.
Preferably, the polymers in the polymer dispersion have a narrow particle size distribution. The particle size distribution is characterized by the polydispersity index, which is a dimensionless number calculated from a simple 2 parameter fit to the correlation data of the cumulant analysis. The calculation is normally done as described in ISO 13321: 1996. Frequently, the PDI will be less than 0.2.
The polymer latex of the carboxylated polymer is usually obtainable by an aqueous radical emulsion polymerization, in particular by free-radical aqueous emulsion polymerization, of the monomers M forming the carboxylated monomer latex by analogy to well-known processes of radical emulsion polymerisation technology, for example from the prior art cited at the outset and from “Emulsionspolymerisation” [Emulsion Polymerization] in Encyclopedia of Polymer Science and Engineering, vol. 8, pages 659 ff. (1987) ; D. C. Blackley, in High Polymer Latices, vol. 1, pages 35 ff. (1966) ; H. Warson, The Applications of Synthetic Resin Emulsions, chapter 5, pages 246 ff. (1972) ; D. Diederich, Chemie in unserer Zeit 24, pages 135 to 142 (1990) ; Emulsion Polymerisation, Interscience Publishers, New York (1965) ; DE-A40 03 422 and Dispersionen synthetischer Hochpolymerer [Dispersions of Synthetic High Polymers] , F. Holscher, Springer-Verlag, Berlin (1969) ] .
According to the present invention, the free-radically initiated aqueous emulsion polymerization is triggered by means of a redox initiator system.
Suitable oxidizing agents for the redox initiator systems can be inorganic peroxides, such as hydrogen peroxide or peroxodisulfates, such as the mono-or di-alkali metal or ammonium salts of peroxodisulfuric acid, for example the mono-and disodium, -potassium or ammonium salts, such as sodium persulfate (NaPs) , or organic peroxides such as alkyl hydroperoxides, for example tert-butyl hydroperoxide (TBHP) , tert-Amyl hydroperoxide (TAHP) , p-menthyl hydroperoxide or cumyl hydroperoxide, and also dialkyl or diaryl peroxides, such as di-tert-butyl or di-cumyl peroxide.
Corresponding reducing agents which may be used for the redox initiator systems are sulfur compounds with a low oxidation state, such as alkali metal sulfites, for example potassium and/or sodium sulfite, alkali metal hydrogensulfites, for example potassium and/or sodium hydrogensulfite such as NaHSO3, alkali metal metabisulfites, for example potassium and/or sodium metabisulfite such as sodium metabisulfite (SMBS) , sodium-acetone bisulfite (SAB) , formaldehydesulfoxylates, for example potassium and/or sodium formaldehydesulfoxylate such as sodium formaldehyde sulfoxylate (SFS) , alkali metal salts, specifically potassium and/or sodium salts of aliphatic sulfinic acids and alkali metal hydrogensulfides, for example potassium and/or sodium hydrogensulfide, salts of polyvalent metals, such as iron (Il) sulfate, iron (Il) ammonium sulfate, iron (Il) phosphate, ene diols, such as dihydroxymaleic acid, benzoin and/or  ascorbic acid, and reducing saccharides, such as Vitamin C (VC) , sorbose, glucose, fructose and/or dihydroxyacetone.
Preferably, the oxidizing agents and the reducing agents for the redox initiator systems can be a combination of tert-butyl hydroperoxide (TBHP) and sodium formaldehyde sulfoxylate (SFS) , a combination of tert-amyl hydroperoxide (TAHP) and sodium formaldehyde sulfoxylate (SFS) , a combination of tert-butyl hydroperoxide (TBHP) and sodium-acetone bisulfite (SAB) , etc.
In general, the amount of the redox initiator system is present in a total amount in the range from 0.1%by weight to 2.5%by weight, preferably in the range from 0.15%by weight to 2%by weight, in particular in the range from 0.2 %by weight to 1.5%by weight, such as 0.3 %by weight, 0.4 %by weight, 0.5 %by weight, 0.6 %by weight, 0.7 %by weight, 0.8 %by weight, 0.9 %by weight, 1.0 %by weight, 1.1%by weight, 1.2 %by weight, 1.3 %by weight, 1.4 %by weight, 1.5 %by weight, 1.6 %by weight, 1.7 %by weight, 1.8 %by weight, 1.9 %by weight, 2.0 %by weight, 2.1%by weight, 2.2 %by weight, 2.3 %by weight, 2.4 %by weight, etc. based on the total weight of the monomer composition M.
The redox initiator system comprises oxidizing agent and reducing agent in a weight ratio in the range from 1: 1 to 10: 1, in particular in the range from 1: 1 to 5: 1, more particular in the range from 1.1: 1 to 3: 1.
The oxidizing agent can be present in an amount in the range from 0.09%by weight to 1.6%by weight, in particular in the range from 0.12%by weight to 1.3%by weight, more particular in the range from 0.15%by weight to 1%by weight based on the total weight of the monomer composition M, such as 0.1%by weight, 0.16%by weight, 0.2%by weight, 0.3%by weight, 0.4%by weight, 0.5%by weight, 0.6%by weight, 0.7%by weight, 0.8%by weight, 0.9%by weight, 1.1%by weight, 1.2%by weight, 1.4%by weight, 1.5%by weight, etc.
The reducing agent is present in an amount in the range from 0.01%by weight to 0.9%by weight, in particular in the range from 0.03%by weight to 0.7%by weight, more particular in the range from 0.05%by weight to 0.5%by weight, based on the total weight of the monomer composition M, such as 0.06%by weight, 0.1%by weight, 0.15%by weight, 0.2%by weight, 0.3%by weight, 0.4%by weight, 0.5%by weight, 0.6%by weight, 0.8%by weight, etc.
The amount of the redox initiator system required in the process of the invention for the emulsion polymerization can be initially charged in the polymerization vessel completely. However, it is also possible to charge none of or merely a portion of the redox initiator, for example not more than 30%by weight, especially not more than 20%by weight, based on the total amount of the redox initiator required in the aqueous polymerization medium and then, under polymerization conditions, during the free-radical emulsion polymerization of the monomer composition M to add the entire amount or any remaining residual amount, according to the consumption, batchwise in one or more portions or continuously with constant or varying flow rates.
Preferably, the radical emulsion polymerization of the monomers forming the carboxylated polymer latex is performed by a so-called feed process, which means that at least 90%, in particular at least 95%or the total amount of the monomers to be polymerised are metered to the polymerisation reaction under polymerisation conditions during a metering period P. The duration of the period P may depend on the production equipment and may vary from e.g., 20 minutes to 12 hours. Frequently, the duration of the period P will be in the range from 0.5 hour to 5 hours, especially from 1 hour to 4 hours.
The term “polymerization conditions” is generally understood to mean those temperatures and pressures under which the free-radically initiated aqueous emulsion polymerization proceeds at sufficient polymerization rate. They depend particularly on the redox initiator used. Advantageously, the type and amount of the redox initiator, polymerization temperature and polymerization pressure are selected such that a sufficient amount of initiating radicals is always present to initiate or to maintain the polymerization reaction. In a preferred embodiment, the redox initiator system is used in an amount high enough to allow over 99%of the monomer composition M is polymerized by redox initiation.
It may be suitable to establish the polymerization conditions and to initially charge at least a portion of the redox initiator into the polymerization vessel before the metering of the monomers M is started.
It has been found advantageous to perform the free-radical emulsion polymerization in the presence of seed latex. A seed latex is a polymer latex which is present in the aqueous polymerization medium before the metering of the monomers M is started.
The seed latex may help to better adjust the particle size or the final polymer latex obtained in the free-radical emulsion polymerization of the invention.
In principle, every polymer latex may serve as seed latex. For the purpose of the invention, preference is given to seed latices, where the particle size of the polymer particles is comparatively small. In particular, the Z average particle diameter of the polymer particles of the seed latex, as determined by dynamic light scattering at 20℃ (see below) is preferably in the range from 10 to 80 nm, in particular from 10 to 50 nm. Preferably, the polymer particles of the seed latex are made of ethylenically unsaturated monomers, which comprise at least 95%by weight, based on the total weight of the monomers forming the seed latex, of one or more monomers M1a and/or M1b as defined above. The polymer particles of the seed latex particularly comprise at least 95%by weight, based on the total weight of the monomers forming the seed latex, of at least one monomer M1b or of a mixture of at least one monomer M1b and one or more monomers M1a, where the proportion of monomers M1b to M1a is at least 1: 2 on a weight basis.
For this, the seed latex is usually charged into the polymerisation vessel before the metering of the monomers M is started. In particular, the seed latex is charged into the polymerisation vessel followed by establishing the polymerization conditions, e.g., by heating the mixture to polymerization temperature. It may be beneficial to charge at least a portion of the redox initiator into the polymerisation vessel before the metering of the monomers M is started. However, it is also possible to meter the monomers and the free-radical polymerization initiator in parallel to the polymerization vessel.
The amount of seed latex, calculated as solids, may frequently be in the range from 0.1 to 10%by weight, in particular from 0.5 to 5%by weight, based on the total weight of the monomers M to be polymerized. The free-radical aqueous emulsion polymerization of the invention can be conducted at temperatures in the range from 0 to 170℃. Temperatures employed are generally in the range from 30 to 120℃, frequently from 40 to 100℃ and often from 40 to 60℃. The free-radical aqueous emulsion polymerization of the invention can be conducted at a pressure of less than, equal to or greater than 1 atm (atmospheric pressure) , and so the polymerization temperature may exceed 100℃ and may be up to 170℃.
Polymerization of the monomers is normally performed at ambient pressure but it may also be performed under elevated pressure. In this case, the pressure may assume values of 1.2, 1.5, 2, 5, 10, 15 bar (absolute) or even higher values. If emulsion polymerizations are conducted under reduced pressure, pressures of 950 mbar, frequently of 900 mbar and often 850 mbar (absolute) are established.
Advantageously, the free-radical aqueous emulsion polymerization of the invention is conducted at ambient pressure (about 1 atm) with exclusion of oxygen, for example under an inert gas atmosphere, for example under nitrogen or argon.
The polymerization of the monomers M can optionally be conducted in the presence of chain transfer agents. Chain transfer agents are understood to mean compounds that transfer free radicals and which reduce the molecular weight of the polymer or control chain growth in the polymerization. Examples of chain transfer agents are aliphatic and/or araliphatic halogen compounds, for example n-butyl chloride, n-butyl bromide, n-butyl iodide, methylene chloride, ethylene dichloride, chloroform, bromoform, bromotrichloromethane, dibromodichloromethane, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide, organic thio compounds, such as primary, secondary or tertiary aliphatic thiols, for example ethanethiol, n-propanethiol, 2-propanethiol, n-butanethiol, 2-butanethiol, 2-methyl-2-propanethiol, n-pentanethiol, 2-pentanethiol, 3-pentanethiol, 2-methyl-2-butanethiol, 3-methyl-2-butanethiol, n-hexanethiol, 2-hexanethiol, 3-hexanethiol, 2-methyl-2-pentanethiol, 3-methyl-2-pentanethiol, 4-methyl-2-pentanethiol, 2-methyl-3-pentanethiol, 3-methyl-3-pentanethiol, 2-ethylbutanethiol, 2-ethyl-2-butanethiol, n-heptanethiol and the isomeric compounds thereof, n-octanethiol and the isomeric compounds thereof, n-nonanethiol and the isomeric compounds thereof, n-decanethiol and the isomeric compounds thereof, n-undecanethiol and the isomeric compounds thereof, n-dodecanethiol and the isomeric compounds thereof, n-tridecanethiol and isomeric compounds thereof, substituted thiols, for example 2-hydroxyethanethiol, aromatic thiols such as benzenethiol, ortho-, meta-or para-methylbenzenethiol, alkylesters of mercaptoacetic acid (thioglycolic acid) , such as 2-ethylhexyl thioglycolate, alkylesters of mercaptopropionic acid, such as octyl mercapto propionate, and also further sulfur compounds described in Polymer Handbook, 3rd edition, 1989, J. Brandrup and E. H. Immergut, John Wiley &Sons, section II, pages 133 to 141, but also aliphatic and/or aromatic aldehydes, such as acetaldehyde, propionaldehyde and/or benzaldehyde, unsaturated fatty acids, such as oleic acid, dienes having nonconjugated double bonds, such as divinylmethane or vinylcyclohexane, or hydrocarbons having readily abstractable hydrogen atoms, for example toluene. Alternatively, it is possible to use mixtures of the aforementioned chain transfer agents that do not disrupt one another. The total amount of chain transfer agents optionally used in the process of the invention, based on the total amount of monomers M, will generally not exceed 1%by weight. However, it is possible, that during a certain period of the polymerization reaction the amount of chain transfer agent added to the polymerization reaction may exceed the value of 1%by weight, based on the total amount of monomers already added to the polymerization reaction.
The free-radical emulsion polymerization of the invention is usually performed in an aqueous polymerization medium, which, as well as water, comprises at least one surface-active substance (surfactant) for stabilizing the emulsion of the monomers and the polymer particles of the polymer latex.
The surfactant may be selected from emulsifiers and protective colloids. Protective colloids, as opposed to emulsifiers, are understood to mean polymeric compounds having molecular  weights above 2000 Daltons, whereas emulsifiers typically have lower molecular weights. The surfactants may be anionic or nonionic or mixtures of non-ionic and anionic surfactants. Anionic surfactants usually bear at least one anionic group, which is selected from phosphate, phosphonate, sulfate, and sulfonate groups. The anionic surfactants, which bear at least one anionic group, are typically used in the form of their alkali metal salts, especially of their sodium salts or in the form of their ammonium salts. Preferred anionic surfactants are anionic emulsifiers, in particular those, which bear at least one sulfate or sulfonate group. Likewise, anionic emulsifiers, which bear at least one phosphate or phosphonate group may be used, either as sole anionic emulsifiers or in combination with one or more anionic emulsifiers, which bear at least one sulfate or sulfonate group.
Examples of anionic emulsifiers, which bear at least one sulfate or sulfonate group, are, for example,
- the salts, especially the alkali metal and ammonium salts, of alkyl sulfates, especially of C8-C22-alkyl sulfates,
- the salts, especially the alkali metal and ammonium salts, of sulfuric monoesters of ethoxylated alkanols, especially of sulfuric monoesters of ethoxylated C8-C22-alkanols, preferably having an ethoxylation level (EO level) in the range from 2 to 40,
- the salts, especially the alkali metal and ammonium salts, of sulfuric monoesters of ethoxylated alkylphenols, especially of sulfuric monoesters of ethoxylated C4-C18-alkylphenols (EO level preferably 3 to 40) ,
- the salts, especially the alkali metal and ammonium salts, of alkylsulfonic acids, especially of C8-C22-alkylsulfonic acids,
- the salts, especially the alkali metal and ammonium salts, of dialkyl esters, especially di-C4-C18-alkyl esters of sulfosuccinic acid,
- the salts, especially the alkali metal and ammonium salts, of alkylbenzenesulfonic acids, especially of C4-C22-alkylbenzenesulfonic acids, and
- the salts, especially the alkali metal and ammonium salts, of mono-or disulfonated, alkyl-substituted diphenyl ethers, for example of bis (phenylsulfonic acid) ethers bearing a C4-C24-alkyl group on one or both aromatic rings. The latter are common knowledge, for example from US-A-4, 269, 749, and are commercially available, for example as 2A1 (Dow Chemical Company) .
Also suitable are mixtures of the aforementioned salts.
Preferred anionic surfactants are anionic emulsifiers, which are selected from the following groups:
- the salts, especially the alkali metal and ammonium salts, of alkyl sulfates, especially of C8-C22-alkyl sulfates,
- the salts, especially the alkali metal salts, of sulfuric monoesters of ethoxylated alkanols, especially of sulfuric monoesters of ethoxylated C8-C22-alkanols, preferably having an ethoxylation level (FO level) in the range from 2 to 40, of sulfuric monoesters of ethoxylated alkylphenols, especially of sulfuric monoesters of ethoxylated C4-C18-alkylphenols (EO level preferably 3 to 40) , of alkylbenzenesulfonic acids, especially of C4-C22-alkylbenzenesulfonic  acids, and of mono-or disulfonated, alkyl-substituted diphenyl ethers, for example of bis (phenylsulfonic acid) ethers bearing a C4-C24-alkyl group on one or both aromatic rings.
Examples of anionic emulsifiers, which bear a phosphate or phosphonate group, include, but are not limited to the following, salts selected from the following groups:
- the salts, especially the alkali metal and ammonium salts, of mono-and dialkyl phosphates, especially C8-C22-alkyl phosphates,
- the salts, especially the alkali metal and ammonium salts, of phosphoric monoesters of C2-C3-alkoxylated alkanols, preferably having an alkoxylation level in the range from 2 to 40, especially in the range from 3 to 30, for example phosphoric monoesters of ethoxylated C8-C22-alkanols, preferably having an ethoxylation level (EO level) in the range from 2 to 40, phosphoric monoesters of propoxylated C8-C22-alkanols, preferably having a propoxylation level (PO level) in the range from 2 to 40, and phosphoric monoesters of ethoxylated-co-propoxylated C8-C22-alkanols, preferably having an ethoxylation level (EO level) in the range from 1 to 20 and a propoxylation level of 1 to 20,
- the salts, especially the alkali metal and ammonium salts, of phosphoric monoesters of ethoxylated alkylphenols, especially phosphoric monoesters of ethoxylated C4-C18-alkylphenols (EO level preferably 3 to 40) ,
- the salts, especially the alkali metal and ammonium salts, of alkylphosphonic acids, especially C8-C22-alkylphosphonic acids and
- the salts, especially the alkali metal and ammonium salts, of alkylbenzenephosphonic acids, especially C4-C22-alkylbenzenephosphonic acids.
Further suitable anionic surfactants can be found in Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry] , volume XIV/1, Makromolekulare Stoffe [Macromolecular Substances] , Georg-Thieme-Verlag, Stuttgart, 1961, p. 192-208.
Preferably, the surfactant comprises at least one anionic emulsifier, which bears at least one sulfate or sulfonate group. The at least one anionic emulsifier, which bears at least one sulfate or sulfonate group, may be the sole type of anionic emulsifiers. However, mixtures of at least one anionic emulsifier, which bears at least one sulfate or sulfonate group, and at least one anionic emulsifier, which bears at least one phosphate or phosphonate group, may also be used. In such mixtures, the amount of the at least one anionic emulsifier, which bears at least one sulfate or sulfonate group, is preferably at least 50%by weight, based on the total weight of anionic surfactants used in the process of the present invention. In particular, the amount of anionic emulsifiers, which bear at least one phosphate or phosphonate group does not exceed 20%by weight, based on the total weight of anionic surfactants used in the process of the present invention.
As well as the aforementioned anionic surfactants, the surfactant may also comprise one or more nonionic surface-active substances, which are especially selected from nonionic emulsifiers. Suitable nonionic emulsifiers are e. g., araliphatic or aliphatic nonionic emulsifiers, for example ethoxylated mono-, di-and trialkylphenols (EO level: 3 to 50, alkyl radical: C4-C10) , ethoxylates of long-chain alcohols (EO level: 3 to 100, alkyl radical: C8-C36) , and polyethylene oxide/polypropylene oxide homo-and copolymers. These may comprise the alkylene oxide units copolymerized in random distribution or in the form of blocks. Very suitable examples are the EO/PO block copolymers. Preference is given to ethoxylates of long-chain alkanols, in  particular to those where the C8-C30 alkyl radical having a mean ethoxylation level of 5 to 100 and, among these, particular preference to those having a linear C12-C20 alkyl radical and a mean ethoxylation level of 10 to 50, and also to ethoxylated monoalkylphenols.
In a particular embodiment of the invention, the surfactants used in the process of the present invention comprise less than 20%by weight, especially not more than 10%by weight, of nonionic surfactants, based on the total amount of surfactants used in the process of the present invention, and especially do not comprise any nonionic surfactant. In another embodiment of the invention, the surfactants used in the process of the present invention comprise at least one anionic surfactant and at least one non-ionic surfactant, the ratio of anionic surfactants to non-ionic surfactants being usually in the range form 0.5: 1 to 10: 1, in particular from 1: 1 to 5: 1.
Preferably, the surfactant will be used in such an amount that the amount of surfactant is in the range from 0.2 to 5%by weight, especially in the range from 0.5 to 3%by weight, based on the monomers M to be polymerized.
The aqueous reaction medium in polymerization may in principle also comprise minor amounts (usually at most 5%by weight) of water-soluble organic solvents, for example methanol, ethanol, isopropanol, butanols, pentanols, but also acetone, etc. Preferably, however, the process of the invention is conducted in the absence of such solvents.
The polymer latex of the carboxylated polymer is for example obtainable by a single stage or by a multistage emulsion polymerization, in particular an aqueous radical emulsion polymerization, of a monomer composition M. The term “multistage” in the context of aqueous emulsion polymerization is well understood to mean that the relative concentration of the monomers in the monomer composition M added to the polymerization reaction is altered at least once during the aqueous emulsion polymerization. Such a procedure results in at least two polymer populations of different monomer compositions in the polymer particles of the latex. For example, it will be possible to change the monomer composition such that the multistage latex polymer features populations having different glass transition temperatures or a glass transition temperature (Tg) gradient. It may also be possible to change the monomer composition such that the multistage latex polymer features populations having different concentrations of polymerized acidic monomers, such as monomers M2 or a concentration gradient of monomers M2. During the addition of the monomers M, the type of monomers and/or the relative amounts thereof can be altered continuously or stepwise. However, it is also possible that the type and relative amounts of monomers M, which are added to the polymerization reaction remains constant. For example, it is possible that the ratio of monomers M1 and M2 increases or decreases during the addition.
The concentration of the polymer latex contained in the aqueous binder composition is frequently in the range from 10 to 70%by weight, in particular in the range from 30 to 65%by weight, especially in the range from 40 to 65%by weight, based in on the total weight of the aqueous binder composition.
The aqueous binder composition usually consists of the aqueous polymer latex of a film forming carboxylated polymer as described herein and the polyetheramine polyol as described herein and water. However, the aqueous binder composition optionally contains further components such as for example dispersants, biocides, and defoamers.
The present invention also relates to water-borne coating compositions containing the aqueous binder composition as defined herein.
Preferred embodiments of the aqueous binder composition contained in the water-borne coating compositions are those mentioned hereinabove.
In addition to the binder composition, the coating compositions preferably further contain at least one pigment and/or at least one filler. However, coating compositions, which do not contain a pigment or filler are also part of the invention.
Pigments for the purposes of the present invention are virtually insoluble, finely dispersed, organic or preferably inorganic colorants as per the definition in German standard specification DIN 55944. Preferably, the composition contains at least one inorganic pigment. Representative examples of organic pigments are
- monoazo pigments, such as C.I. Pigment Brown 25; C.I. Pigment Orange 5, 13, 36 and 67; C.I. Pigment Red 1, 2, 3, 5, 8, 9, 12, 17, 22, 23, 31, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 52: 1, 52: 2, 53, 53: 1, 53: 3, 57: 1, 63, 112, 146, 170, 184, 210, 245 and 251; C.I. Pigment Yellow 1, 3, 73, 74, 65, 97, 151 and 183;
- diazo pigments, such as C.I. Pigment Orange 16, 34 and 44; C.I. Pigment Red 144, 166, 214 and 242; C.I. Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 and 188;
- anthanthrone pigments, such as C.I. Pigment Red 168 (C.I. Vat Orange 3) ; anthraquinone pigments, such as C.I. Pigment Yellow 147 and 177; C.I. Pigment Violet 31;
- anthraquinone pigments, such as C.I. Pigment Yellow 147 and 177; C.I. Pigment Violet 31;
- anthrapyrimidine pigments, such as C.I. Pigment Yellow 108 (C.I. Vat Yellow 20) ; quinacridone pigments, such as C.I. Pigment Red 122, 202 and 206; C.I. Pigment Violet 19;
- quinophthalone pigments, such as C.I. Pigment Yellow 138;
- dioxazine pigments, such as C.I. Pigment Violet 23 and 37;
- flavanthrone pigments, such as C.I. Pigment Yellow 24 (C.I. Vat Yellow 1) ;
- indanthrone pigments, such as C.I. Pigment Blue 60 (C.I. Vat Blue 4) and 64 (C.I. Vat Blue 6) ;
- isoindoline pigments, such as C.I. Pigment Orange 69; C.I. Pigment Red 260; C.I. Pigment Yellow 139 and 185;
- isoindolinone pigments, such as C.I. Pigment Orange 61; C.I. Pigment Red 257 and 260; C.I. Pigment Yellow 109, 110, 173 and 185;
- isoviolanthrone pigments, such as C.I. Pigment Violet 31 (C.I. Vat Violet 1 ) ;
- metal complex pigments, such as C.I. Pigment Yellow 117, 150 and 153; C.I. Pigment Green 8;
- perinone pigments, such as C.I. Pigment Orange 43 (C.I. Vat Orange 7) ; C.I. Pigment Red 194 (C.I. Vat Red 15) ;
- perylene pigments, such as C.I. Pigment Black 31 and 32; C.I. Pigment Red 123, 149, 178, 179 (C.I. Vat Red 23) , 190 (C.I. Vat Red 29) and 224; C.I. Pigment Violet 29;
- phthalocyanine pigments, such as C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and 16; C.I. Pigment Green 7 and 36;
- pyranthrone pigments, such as C.I. Pigment Orange 51; C.I. Pigment Red 216 (C.I. Vat Orange 4) ;
- thioindigo pigments, such as C.I. Pigment Red 88 and 181 (C.I. Vat Red 1 ) ; C.I. Pigment Violet 38 (C.I. Vat Violet 3) ;
- triarylcarbonium pigments, such as C.I. Pigment Blue 1, 61 and 62; C.I. Pigment Green 1; C.I. Pigment Red 81, 81: 1 and 169; C.I. Pigment Violet 1, 2, 3 and 27; C.I. Pigment Black 1 (aniline black) ;
- C.I. Pigment Yellow 101 (aldazine yellow) , and C.I. Pigment Brown 22.
Specific examples of preferred organic pigments are C.I. Pigment Yellow 138, C.I. Pigment Red 122, C.I. Pigment Violet 19, C.I. Pigment Blue 15: 3 and 15: 4, C.I. Pigment Black 7, C.I. Pigment Orange 5, 38 and 43, and C.I. Pigment Green 7.
Preferred are inorganic pigments, for example
- white pigments such as titanium dioxide (C.I. Pigment White 6) , zinc white, pigment grade zinc oxide; zinc sulfide, lithopone; lead white; furthermore white fillers such as barium sulfate and CaCO3 which are also referred to as inorganic white pigments in the context of the present invention,
- black pigments, such as iron oxide black (C.I. Pigment Black 11 ) , iron manganese black, spinel black (C.I. Pigment Black 27) , carbon black (C.I. Pigment Black 7) ;
- color pigments, such as chromium oxide, chromium oxide hydrate green; chrome green (C.I. Pigment Green 48) ; cobalt green (C.I. Pigment Green 50) ; ultramarine green; cobalt blue (C.I. Pigment Blue 28 und 36) ; ultramarine blue, iron blue (C.I. Pigment Blue 27) , manganese blue, ultramarine violet, cobalt violet, manganese violet, iron oxide read (C.I. Pigment Red 101) ; cadmium sulfoselenide (C.I. Pigment Red 108) ; molybdate red (C.I. Pigment Red 104) ; ultramarine red;
- iron oxide brown, mixed brown, spinel-and Korundum phases (C.I. Pigment Brown 24, 29 und 31 ) , chrome orange;
- iron oxide yellow (C.I. Pigment Yellow 42) ; nickel titanium yellow (C.I. Pigment Yellow 53; C.I. Pigment Yellow 157 und 164) ; chrome titanium yellow; cadmium sulfide und cadmium zinc sulfide (C.I. Pigment Yellow 37 und 35) ; Chrome yellow (C.I. Pigment Yellow 34) , zinc yellow, alkaline earth metal chromates; Naples yellow; bismuth vanadate (C.I. Pigment Yellow 184) ;
- Interference pigments, such as metallic effect pigments based on coated metal platelets, pearl luster pigments based on mica platelets coated with metal oxide, and liquid crystal pigments.
Preferred inorganic pigments are selected from inorganic yellow pigments and inorganic white pigments, especially titanium dioxide, barium sulfate, and CaCO3.
The compositions can also comprise mixtures of two or more different pigments, in which case it is preferable that at least one pigment be inorganic. The pigments are usually in particulate form, i.e., in the form of particles. Pigments can be selected from crude pigments, i. e., untreated as- synthesized pigments. The particles of pigment may be regular or irregular in shape in that, for example, the particles may have a spherical or substantially spherical shape or a needle (acicular) shape.
In one embodiment of the present invention, the pigment is in spherical or substantially spherical shape, i. e., the ratio of the longest diameter to the smallest diameter is in the range from 1.0 to 2.0, preferably up to 1.5. In one embodiment of the present invention, the pigment has an average particle diameter (median, d50) in the range of from 20 to 50 pm, measured, e.g., by Coulter counter or with a Hegman gauge.
Examples of suitable fillers are aluminosilicates, such as feldspars, silicates, such as kaolin, talc, mica, magnesite, alkaline earth metal carbonates, such as calcium carbonate, for example in the form of calcite or chalk, magnesium carbonate, dolomite, alkaline earth metal sulfates, such as calcium sulfate, silicon dioxide, etc. In the coating compositions of the invention, finely divided fillers are naturally preferred. The fillers may be used in the form of individual components. In practice, however, filler mixtures have been found to be particularly useful, for example calcium carbonate/kaolin, calcium carbonate/talc. Gloss paints generally comprise only small amounts of very finely divided fillers, or do not comprise any fillers. Fillers also include flatting agents which significantly impair the gloss as desired. Flatting agents are generally transparent and may be either organic or inorganic. Examples of flatting agents are inorganic silicates, for example the 
Figure PCTCN2024094649-ftappb-I100002
brands from W.R. Grace &Company and the 
Figure PCTCN2024094649-ftappb-I100003
brands from Evonik GmbH. Organic flatting agents are obtainable, for example, from BYK-Chemie GmbH under the 
Figure PCTCN2024094649-ftappb-I100004
brands and the 
Figure PCTCN2024094649-ftappb-I100005
brands, and from Deuteron GmbH under the Deuteron 
Figure PCTCN2024094649-ftappb-I100006
brand.
The proportion of the pigments and fillers in coating compositions can be described in a manner known per se via the pigment volume concentration (PVC) . The PVC describes the ratio of the volume of pigments (VP) and fillers (VF) relative to the total volume, consisting of the volumes of binder (VB) , pigments (VP) and fillers (VF) in a dried coating film in percent: PVC = (VP + VF) x 100 / (VP + VF + VB) .
The compositions usually have a pigment volume concentration (PVC) of at least 5, especially at least 10. Preferably, the PVC will not exceed a value of 60, especially 40, and is specifically in the range from 5 to 60 or 5 to 40. However, the inventive effects of the polymer dispersions are also manifested in varnishes which typically have a pigment/filler content below 5 %by weight, based on the varnish, and correspondingly have a PVC below 5.
The water-borne coating compositions of the invention may also comprise customary auxiliaries. The customary auxiliaries will depend on the kind of the coating in a well-known manner and include but are not limited to:
rheology modifying agents,
wetting agents or dispersants,
filming auxiliaries,
levelling agents,
biocides, and
defoamers.
Suitable rheology modifying agents include associative thickener polymers and non-associative rheology modifiers. Suitable associative thickener polymers include anionic associate thickeners such as hydrophobically modified acrylate thickeners, also termed HASE thickeners, and nonionic associative thickeners, also termed NiSAT type associative thickeners, including the hydrophobically modified polyethylene oxide urethane rheology modifiers, also termed HEUR or PUR thickeners, and hydrophobically modified polyethyleneoxides, which are also termed HMPE. Suitable non-associative rheology modifiers are in particular cellulose based thickeners, especially hydroxyethyl cellulose, but also thickeners based on acrylate emulsions (ASE) . Preference is given to non-associative cellulose based thickeners. The amount of the thickener polymer will depend on the desired viscosity profile and is frequently in the range from 0.05 to 2.5%by weight, in particular 0.1 to 2%by weight of thickener, and especially 0.15 to 1.5%by weight, based on the latex paint.
Suitable wetting agents or dispersants are, for example, sodium polyphosphates, potassium polyphosphates or ammonium polyphosphates, alkali metal salts and ammonium salts of acrylic acid copolymers or maleic anhydride copolymers, polyphosphonates, such as sodium 1-hydroxyethane-1, 1-diphosphonate, and naphthalenesulfonic salts, especially the sodium salts thereof.
Suitable filming auxiliaries are solvents and plasticizers. Plasticizers, in contrast to solvents, have a Iow volatility and preferably have a boiling point at 1013 mbar of higher than 250℃ while solvents have a higher volatility than plasticizers and preferably have a boiling point at 1013 mbar of less than 250℃. Suitable filming auxiliaries are, for example, white spirit, pine oil, propylene glycol, ethylene glycol, butyl glycol, butyl glycol acetate, butyl glycol diacetate, butyl diglycol, butylcarbitol, 1-methoxy-2-propanol, 2, 2, 2-trimethyl-1, 3-pentanediol monoisobutyrate 
Figure PCTCN2024094649-ftappb-I100007
and the glycol ethers and esters, commercially available, for example, from BASF SE under the 
Figure PCTCN2024094649-ftappb-I100008
and 
Figure PCTCN2024094649-ftappb-I100009
names, and from Dow under the 
Figure PCTCN2024094649-ftappb-I100010
trade name. The amount is preferably ＜ 10%by weight and more preferably ＜ 5%by weight, based on the overall formulation. Formulation is also possible completely without solvents.
Further formulation ingredients for water-borne paints are described in detail in M. Schwartz and R. Baumstark “Water-based Acrylates for Decorative Coatings” , Curt R. Vincentz Verlag, Hanover, 2001, p. 191-212 (ISBN 3-87870-726-6) .
A further embodiment of the present invention are methods of producing a coating on a surface comprising
(a) applying the aqueous binder composition as described herein and/or the water-borne coating composition as described herein to the surface, and
(b) allowing the composition to dry to produce the coating.
The composition can be applied to surfaces and/or substrates to be coated in a customary manner such as for example by applying the paint with brushes or rolls, by spraying, by dipping, by rolling, or by bar coating. The coating of surfaces and/or substrates is effected in such a way that the surface and/or substrate is first coated with a composition of the invention and then the aqueous composition is subjected to a drying step.
The composition can be applied to surfaces such as for example metal, asphalt, concrete, fiber boards, stone, ceramic, minerals, wood, plastic, polymer, and glass. The composition can be applied to interior or exterior surfaces such as for example an architectural surface such as a  roof, a wall, a floor, and a ceiling. Preferably, the composition can be applied to exterior surfaces.
Embodiment
Although the following detailed description gives specific preferred embodiments, the persons skilled in the art should understand that these embodiments are only for example and the present invention can be practiced in alternative ways.
1. An aqueous binder composition comprising
(a) an aqueous polymer latex of a carboxylated polymer;
(b) a polyetheramine polyol dissolved in the polymer latex, wherein at least 20wt%of the amino groups among all the amino groups in the polyetheramine polyol are tertiary amine groups;
wherein the carboxylated polymer is obtainable by a radical emulsion polymerization of a monomer composition M using a reduction-oxidation initiator system, where the monomer composition M comprises:
i) 70%by weight to 99.95%by weight, based on the total weight of the monomer composition M, of one or more ethylenically unsaturated monomers M1, which are selected from C1-C20-alkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, di-C1-C20-alkyl esters of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, C5-C20-cycloalkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, vinylesters of C1-C20-alkanoic acids, vinyl aromatic monomers, C2-C6-monoolefines and conjugated dienes; and
ii) 0.05%by weight to 30%by weight, based on the total weight of the monomer composition M, of one or more ethylenically unsaturated monomers M2, which are selected from ethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms and ethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms.
2. The binder composition according to embodiment 1, wherein the polyetheramine polyol contains on average from 1 to 8.2 mol/kg of tertiary amino groups.
3. The binder composition according to any one of the preceding embodiments, wherein the polyetheramine polyol is a branched polyetheramine polyol.
4. The binder composition according to any one of the preceding embodiments, wherein the polyetheramine polyol has a weight-average molecular weight Mw in the range of 1000 to 300000 g/mol, in particular in the range from 2000 to 200000 g/mol, and especially in the range from 5000 to 150000 g/mol.
5. The binder composition according to any one of the preceding embodiments, wherein the monomer composition M further comprises one or more non-ionic monomers M3, which are different from monomers M 1.
6. The binder composition according to any one of the preceding embodiments, wherein the monomers M1 are a mixture of
- at least one monomer M1a, selected from C1-C20-alkyl esters of acrylic acid, C5-C20-alkylesters of methacrylic acid and mixtures thereof; and
- at least one monomer M1b, selected from vinyl aromatic monomers, C1-C4-alkyl esters of methacrylic acid and mixtures thereof.
7. The binder composition according to any one of the preceding embodiments, wherein the monomer M2 is selected from acrylic acid, methacrylic acid, and mixtures thereof.
8. The binder composition according to any one of the preceding embodiments, wherein the monomer composition M comprises from 95 to 99%by weight of monomer M1 and from 1 to 5%by weight of monomer M2.
9. The binder composition according to any one of the preceding embodiments, wherein the reduction-oxidation initiator system is composed of at least one reducing agent and at least one oxidizing agent.
10. The binder composition according to any one of the preceding embodiments, wherein the reduction-oxidation initiator system is present in a total amount in the range from 0.1%by weight to 2.5%by weight, in particular in the range from 0.15%by weight to 2%by weight, more particular in the range from 0.2 %by weight to 1.5%by weight based on the total weight of the monomer composition M.
11. The binder composition of any one of the preceding embodiments, wherein the polyetheramine polyol is present in an amount in the range from 0.01%by weight to 10%by weight, in particular in the range from 0.05%by weight to 7.5%by weight, more particular in the range from 1%by weight to 5%by weight based on the dry weight of the carboxylated polymer.
12. A water-borne coating composition containing the aqueous binder composition according to any one of the preceding embodiments.
13. The use of the aqueous binder composition according to any one of embodiments 1 to 11 as a binder or co-binder in a water-borne coating composition.
EXAMPLES
The invention is described in more practical terms below by means of illustrative examples, but the invention is not limited in any way by these illustrative examples.
The materials used in the examples are present below:
Tert-butyl hydroperoxide (TBHP)          BASF
Sodium formaldehyde sulfoxylate (SFS)    BASF
Sodium persulfate (NaPS)                 ABC UNITED-INITIATORS HEFEI LIMITED COMPANY
Sodium-acetone bisulfite (SAB)           BASF
tert-amyl hydroperoxide (TAHP)         BASF
Triethanolamine (TEA, 100%)            Sinopharm
Acrylic acid (AA)                      BASF
n-Butyl acrylate (nBA)                 BASF
Ammonia                                BASF
Disponil FES 27                        an emulsifier from BASF
Dissolvine E-FE-13                     a coupling agent from AkzoNobel
Silquest A187                          a silane agent from Momentive
Seed 6772                              an aqueous polystyrene seed dispersion, solid content of 33 wt%,  from  BASF Advanced Chemicals Co. Ltd
Baxxdour EC302                         Polyethyleneimine, 100 wt%in water, from BASF,
Polystar 25                            Polyetheramine polyol (＞90% tertiary amine groups, 10000～60000 g/mol Mw average) , 25 wt% in water, from BASF
Lupasol SC61                           Polyetheramine polyol (＞20% tertiary  amine groups, 100000～150000 Mw average) , 37 wt%in water, from BASF
Determination method
1. The solids content was determined by drying a defined amount of the aqueous polymer dispersion (about 2 g) to constant weight in an aluminum crucible having an internal diameter of about 5 cm at 120℃ in a drying cabinet (about 2 hours) . Two separate measurements were conducted. The value reported in the example is the mean of the two measurements.
2. The particle diameter of the polymer latex was determined by dynamic light scattering of an aqueous polymer dispersion diluted with deionized water to 0.001 to 0.5%by weight at 22℃ by means of a High Performance Particle Sizer (HPPS) from Malvern Instruments, England. What is reported is the cumulant Z average diameter calculated from the measured autocorrelation function (ISO Standard 13321) .
3. The glass transition temperature was determined by the DSC method (Differential Scanning Calorimetry, 20 K/min, midpoint measurement, DIN 53765: 1994-03) by means of a DSC instrument (Q 2000 series from TA instruments) .
4. The molecular weight was determined by GPC using a refractometer as the detector. The mobile phase used was hexafluoroisopropanol (HFIP) , the standard employed for determining the molecular weight being polymethylmethacrylate (PMMA) .
5. The OH number of the polyether amine polyol was determined in accordance with DIN 53240, part 2.
6. The dynamic viscosity of the polyetheramine polyol was determined at 23℃ and a shear rate of 100 sec-1 according to ASTM D7042.
7. The amine number was determined by a standard protocol according to DIN EN ISO 9702: 1998.
8. The elongation at break and tensile strength were determined by a standard protocol according to Singapore Standards SS 500: 2015 (2021) .
9. The early rain resistance test was carried out by spreading a paint film with a thickness of 100μm on black leneta paper, curing under 5℃/90%RH condition for 20 minutes, then rinsing by waterflow with different flowrate for 5 minutes, wherein “Small rain” represents waterflow of 400g/min and “Heavy rain” represents waterflow of 7000g/min. “PASS” represents no film break found after waterflow rinsing. “FAIL” represents film had break after waterflow rinsing.
Preparation Examples
Example 1 to 16, preparation of an aqueous binder composition
Example 1
DI water 195.9g, Seed 6772 35.8g was loaded into a reactor and the reactor was heated up to 60℃. During heating, DI water 167.6g, Disponil FES27 33.7g, AA 10.10g, styrene 226.1g and nBA 235.9g were all mixed together as a pre-emulsion. When the reactor temperature was stable at 60℃, 10%TBHP 7.2g, 5%Dissolvine E-FE-13 1.5g and 1%SFS 7.2g were shotted into the reactor one by one. After 10 minutes, the pre-emulsion was fed for 150 minutes and 1%SFS 21.2g was fed for 165 minutes simultaneously, and post polymerization was performed for 15 minutes after completing feeding SFS. Then 5.7g ammonia (25%) was added for 20 minutes. After neutralization, 10%TBHP 7g and 10%SFS 8g were fed for 60 minutes simultaneously to obtain an aqueous polymer latex of a carboxylated polymer. Then the reactor was cooled down to room temperature, and then ammonia (25%) 5.7g, Silquest A187 1.9g and Polystar 25 20g were added one by one.
Example 2
Example 2 was carried out in the same manner as Example 1, with the exception that the reactor temperature was 50℃, instead of 60℃.
Example 3
Example 3 was carried out in the same manner as Example 1, with the exception that the reactor temperature was 40℃, instead of 60℃.
Example 4
Example 4 was carried out in the same manner as Example 1, with the exception that SAB was used in place of SFS.
Example 5
Example 5 was carried out in the same manner as Example 1, with the exception that TAHP was used in place of TBHP.
Example 6
DI water 195.9g, Seed 6772 35.8g was loaded into a reactor and the reactor was heated up to 60℃. During heating, DI water 167.6g, Disponil FES27 33.7g, AA 10.10g, styrene 226.1g and nBA 235.9g were all mixed together as a pre-emulsion. When the reactor temperature was stable at 60℃, 53%TBHP 7.2g, 5%Dissolvine E-FE-13 1.5g and 5%SFS 7.2g were shotted into the reactor one by one. After 10 minutes, the pre-emulsion was fed for 150 minutes and 5%SFS 21.2g was fed for 165 minutes simultaneously, and post polymerization was performed for 15 minutes after completing feeding SFS. Then 5.7g ammonia (25%) was added for 20 minutes. After neutralization, 10%TBHP 7g and 10%SFS 8g were fed for 60 minutes simultaneously to obtain an aqueous polymer latex of a carboxylated polymer. Then the reactor was cooled down to room temperature, and then ammonia (25%) 5.7g, Silquest A187 1.9g and Polystar 25 20g were added one by one.
Example 7
Example 7 was carried out in the same manner as Example 1, with the exception that 30g Polystar 25 was used.
Example 8
Example 8 was carried out in the same manner as Example 1, with the exception that Lupasol SC61 was used in place of Polystar 25.
Example 9
Example 9 was carried out in the same manner as Example 1, with the exception that no Polystar 25 was used. This example is comparative example.
Example 10
DI water 195.9g, Seed 6772 35.8g was loaded into a reactor and the reactor was heated up to 60℃. During heating, DI water 167.6g, Disponil FES27 33.7g, AA 10.10g, styrene 226.1g and nBA 235.9g were all mixed together as a pre-emulsion. When the reactor temperature was stable at 60℃, 53%TBHP 18g, 5%Dissolvine E-FE-13 1.5g and 10%SFS 12g were shotted into the reactor one by one. After 10 minutes, the pre-emulsion was fed for 150 minutes and 10%SFS 36g was fed for 165 minutes simultaneously, and post polymerization was performed for 15 minutes after completing feeding SFS. Then 5.7g ammonia (25%) was added for 20  minutes. After neutralization, 10%TBHP 7g and 10%SFS 8g were fed for 60 minutes simultaneously to obtain an aqueous polymer latex of a carboxylated polymer. Then the reactor was cooled down to room temperature, and then ammonia (25%) 5.7g, Silquest A187 1.9g and Polystar 25 20g were added one by one.
This example is a comparative example.
Example 11
DI water 195.9g, Seed 6772 35.8g was loaded into a reactor and the reactor was heated up to 60℃. During heating, DI water 167.6g, Disponil FES27 33.7g, AA 10.10g, styrene 226.1g and nBA 235.9g were all mixed together as a pre-emulsion. When the reactor temperature was stable at 60℃, 10%TBHP 4.8g, 5%Dissolvine E-FE-13 1.5g and 0.1%SFS 1.2g were shotted into the reactor one by one. After 10 minutes, the pre-emulsion was fed for 150 minutes and 0.1%SFS 3.5g was fed for 165 minutes simultaneously. The polymerization cannot be started since there is no exothermal phenomenon. Therefore, dispersion could not be made successfully.
This example is a comparative example.
Example 12
DI water 195.9g, Seed 6772 35.8g was loaded into a reactor and the reactor was heated up to 85℃. During heating, DI water 167.6g, Disponil FES27 33.7g, AA 10.10g, styrene 226.1g and nBA 235.9g were all mixed together as a pre-emulsion. When the reactor temperature was stable at 85℃, 7%NaPS 6.9g was shotted into the reactor one by one. After 10 minutes, the pre-emulsion was fed for 150 minutes and 7%NaPS 20.2g was fed for 165 minutes simultaneously, and post polymerization was performed for 15 minutes after completing feeding SFS. Then 5.7g ammonia (25%) was added for 20 minutes. After neutralization, 10%TBHP 7g and 10%SFS 8g were fed for 60 minutes simultaneously. However, the dispersion was found with too much coagulum, no stable dispersion could be obtained.
This example is a comparative example.
Example 13
DI water 195.9g, Seed 6772 35.8g was loaded into a reactor and the reactor was heated up to 85℃. During heating, DI water 167.6g, Disponil FES27 33.7g, AA 10.10g, styrene 226.1g and nBA 235.9g were all mixed together as a pre-emulsion. When the reactor temperature was stable at 85℃, 7%NaPS 17.3g were shotted into the reactor one by one. After 10 minutes, the pre-emulsion was fed for 150 minutes and 7%NaPS 50.5g was fed for 165 minutes simultaneously, and post polymerization was performed for 15 minutes after completing feeding SFS. Then 5.7g ammonia (25%) was added for 20 minutes. After neutralization, 10%TBHP 7g and 10%SFS 8g were fed for 60 minutes simultaneously to obtain an aqueous polymer latex of a carboxylated polymer. Then the reactor was cooled down to room temperature, and then ammonia (25%) 5.7g, Silquest A187 1.9g and Polystar 25 20g were added one by one.
This example is a comparative example.
Example 14
Example 14 was carried out in the same manner as Example 13, with the exception that no Polystar 25 was used.
This example is a comparative example.
Example 15
Example 15 was carried out in the same manner as Example 1, with the exception that Baxxdour EC302 was used in place of Polystar 25.
This example is a comparative example.
Example 16
Example 16 was carried out in the same manner as Example 1, with the exception that triethanolamine (TEA) was used in place of Polystar 25.
This example is a comparative example.
Preparation of a water-borne coating composition
Formulate 400 g of the aqueous binder composition as prepared in each Example 1 to 16 with 95 g of demineralized DI-water, 5 g of dispersant “Dispex A4040“ from BASF, 1 g of wetting agent “Hydropalat 4480“ from BASF, 2.5 g of defoamer “Foamaster MO2150“ from BASF, 3g of thickener “Natrosol 250HBR“ from Ashland, 1.5g of pH adjustor “AMP95“ from ANGUS, 30g of TiO2 “R902+“ from Dupant, 305 g of CaCO3from Omya, 15 g of coalescent from Eastman, and 5 g of cosolvent propylene glycol from Sinopharm Reagent Company, 2g thickener of “50%Rheovis PU1251“ from BASF and 1g “50%Rheovis HS1181“ from BASF. 1000g water-borne coating composition of each Example 1 to 16 was made after water compensation. The coating composition of each example was applied as a 100pm thick coating on black leneta paper for testing.
Results
The percentage of oxidizing agent and reducing agent and polyetheramine polyol/polyethyleneimine/triethanolamine used in the water-borne coating composition of each Example are shown in Table 1 below. Further, the results of Early Rain Resistance (ERR) and tensile properties of the water-borne coating composition are shown in Table 1 below.
*weight percentage based on the total weight of the monomer composition M.
**comparative examples
***no stable dispersion obtained
It can be seen from Table 1 that the inventive coating samples can withstand washing by rain and show good tensile properties. In contrast, the comparative coating samples cannot withstand washing by heavy rain, even though the comparative coating samples of Examples 10 and 13 can withstand washing by small rain. And the elongation at break and tensile strength of the comparative coating samples of Examples 10 and 13 are much lower than the inventive coating samples.
It will be apparent to one person skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the present invention. It is intended that the embodiments and examples be considered as exemplary only. Thus, it is intended that the present invention covers such modifications and variations as come within the scope of the appended claims and their equivalents.

Claims (13)

  1. An aqueous binder composition comprising
    (a) an aqueous polymer latex of a carboxylated polymer;
    (b) a polyetheramine polyol dissolved in the polymer latex, wherein at least 20wt%of the amino groups among all the amino groups in the polyetheramine polyol are tertiary amine groups;
    wherein the carboxylated polymer is obtainable by a radical emulsion polymerization of a monomer composition M using a reduction-oxidation initiator system, where the monomer composition M comprises:
    i) 70%by weight to 99.95%by weight, based on the total weight of the monomer composition M, of one or more ethylenically unsaturated monomers M1, which are selected from C1-C20-alkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, di-C1-C20-alkyl esters of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, C5-C20-cycloalkyl esters of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, vinylesters of C1-C20-alkanoic acids, vinyl aromatic monomers, C2-C6-monoolefines and conjugated dienes; and
    ii) 0.05%by weight to 30%by weight, based on the total weight of the monomer composition M, of one or more ethylenically unsaturated monomers M2, which are selected from ethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms and ethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms.
  2. The binder composition according to claim 1, wherein the polyetheramine polyol contains on average from 1 to 8.2 mol/kg of tertiary amino groups.
  3. The binder composition according to any one of the preceding claims, wherein the polyetheramine polyol is a branched polyetheramine polyol.
  4. The binder composition according to any one of the preceding claims, wherein the polyetheramine polyol has a weight-average molecular weight Mw in the range of 1000 to 300000 g/mol, in particular in the range from 2000 to 200000 g/mol, and especially in the range from 5000 to 150000 g/mol.
  5. The binder composition according to any one of the preceding claims, wherein the monomer composition M further comprises one or more non-ionic monomers M3, which are different from monomers M1.
  6. The binder composition according to any one of the preceding claims, wherein the monomers M1 are a mixture of
    - at least one monomer M1a, selected from C1-C20-alkyl esters of acrylic acid, C5-C20-alkylesters of methacrylic acid and mixtures thereof; and
    - at least one monomer M1b, selected from vinyl aromatic monomers, C1-C4-alkyl esters of methacrylic acid and mixtures thereof.
  7. The binder composition according to any one of the preceding claims, wherein the monomer M2 is selected from acrylic acid, methacrylic acid, and mixtures thereof.
  8. The binder composition according to any one of the preceding claims, wherein the monomer composition M comprises from 95 to 99%by weight of monomer M1 and from 1 to 5%by weight of monomer M2.
  9. The binder composition according to any one of the preceding claims, wherein the reduction-oxidation initiator system is composed of at least one reducing agent and at least one oxidizing agent.
  10. The binder composition according to any one of the preceding claims, wherein the reduction-oxidation initiator system is present in a total amount in the range from 0.1%by weight to 2.5%by weight, in particular in the range from 0.15%by weight to 2%by weight, more particular in the range from 0.2 %by weight to 1.5%by weight based on the total weight of the monomer composition M.
  11. The binder composition of any one of the preceding claims, wherein the polyetheramine polyol is present in an amount in the range from 0.01%by weight to 10%by weight, in particular in the range from 0.05%by weight to 7.5%by weight, more particular in the range from 1%by weight to 5%by weight based on the dry weight of the carboxylated polymer.
  12. A water-borne coating composition containing the aqueous binder composition according to any one of the preceding claims.
  13. The use of the aqueous binder composition according to any one of claims 1 to 11 as a binder or co-binder in a water-borne coating composition.
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