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WO2025036959A1 - Latex polymère aqueux de copolymères approprié comme liant dans des compositions de revêtement à base d'eau - Google Patents

Latex polymère aqueux de copolymères approprié comme liant dans des compositions de revêtement à base d'eau Download PDF

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Publication number
WO2025036959A1
WO2025036959A1 PCT/EP2024/072966 EP2024072966W WO2025036959A1 WO 2025036959 A1 WO2025036959 A1 WO 2025036959A1 EP 2024072966 W EP2024072966 W EP 2024072966W WO 2025036959 A1 WO2025036959 A1 WO 2025036959A1
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weight
monomers
total amount
acrylate
monomer
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PCT/EP2024/072966
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English (en)
Inventor
Friederike Fleischhaker
Andrea Misske
Christoph Fleckenstein
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Basf Se
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Publication of WO2025036959A1 publication Critical patent/WO2025036959A1/fr

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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
    • 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
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate

Definitions

  • Aqueous polymer latex of copolymers suitable as binder in waterborne coating compositions are provided.
  • the present invention relates to aqueous polymer latices of copolymers obtainable by aqueous emulsion polymerisation of ethylenically unsaturated monomers M, which comprise a combination of (meth)acrylate esters as monomers.
  • the present invention also relates to a process for producing such polymer latices and to the use of these polymer latices as binders in waterborne coating compositions.
  • the present invention relates to a waterborne coating composition which contains a binder polymer in the form of the aqueous polymer latex, as defined herein, and at least one further ingredient, which is conventionally used in waterborne coating compositions and which is not a binder.
  • Polymer latices also referred to as polymer dispersions, are commonly known in particular as a binder or binder component, also termed co-binder, for coating compositions.
  • a binder or co-binder in coating compositions, one of the important requirements is that they provide hardness and adherence of the coating to the coated surface.
  • the polymer latex should provide good opacity, good wet scrub resistance, good stain removal properties and low dirt pick-up as well as low water uptake.
  • bio-based means that the monomers are at least partly prepared from renewable raw materials, such as plants, parts of plants, plant waste, biomass and the like. These products are referred to as biobased and are characterized by having a traceable content of 14 C carbon. It is also possible that these materials are converted into suitable feeds, such as bio-naphtha as e.g.
  • Such feeds typically enter the chemical production system, such as a steam cracker, where they are converted into products along the chemical value chain, such as acrylic acid, methacrylic acid, acrylic esters, methacrylic esters and others.
  • the content of renewable material of these products is defined by the mass balance approach and can be allocated to these products.
  • WO 2014/207389 describes the use of 2-octyl acrylate from renewable resources in the production of a polymer latex.
  • the polymer latex is suggested as a binder.
  • WO 2022/018013 describes polymer latices based on acrylate monomers, methacrylate monomers and/or monovinyl aromatic monomers which contain a certain quantity of monomers selected from isobutyl acrylate and isoamyl acrylate and mixtures thereof.
  • the coating compositions prepared therefrom result in coatings having improved the coating properties such as whitening resistance, water-uptake and flexibility of the coating.
  • Isobutyl acrylate and isoamyl acrylate can be - at least with regard to their alkanol part - obtained from biological sources and thus allow for the reduction of fossil carbon in the polymer latices.
  • polymer latices which are at least partly based on bio-based monomers and which have an acceptable or improved application profile which renders them suitable as binders in waterborne coating compositions, in particular in waterborne coating compositions for exterior and interior application.
  • 1-heptyl acrylate can be - at least with regard to its alkanol part - obtained from biological sources and thus allow for the reduction of fossil carbon in the polymer latices.
  • the combination of 1-heptyl acrylate with isobutyl acrylate is particularly suitable to achieve the aforementioned benefits and to allow for replacing conventional acrylate monomers by bio-based monomers.
  • the present invention therefore relates to aqueous polymer latices of copolymers obtainable by aqueous emulsion polymerisation of ethylenically unsaturated monomers M, which comprise i. 5 to 90% by weight, in particular 10 to 70% by weight, especially 10 to 50% by weight, based on the total amount of monomers M, of a monomer M1, which is 1- heptyl acrylate; ii.
  • the present invention also relates to a process for producing the aqueous polymer latices of the present invention.
  • the process comprises performing an aqueous emulsion polymerisation of the monomers M.
  • the present invention also relates to the use of these polymer latices as binders in waterborne coating compositions and waterborne adhesive compositions, in particular as binders in waterborne coating compositions.
  • the present invention relates to waterborne coating compositions which contain a) a binder polymer in the form of the aqueous polymer latex as defined herein; and b) at least one further ingredient, which is conventionally used in waterborne coating compositions and which is not a binder.
  • the present invention is associated with several benefits.
  • the polymer latices are stable and provide a good and well balanced application profile to waterborne coating compositions, such as improved hardness, improved adhesion properties such as high wet and dry alkyd adhesion, low dirt pick-up, improved scrub resistance and good opacity. Since the polymer latices contain considerable amounts of monomers M1, M2 and M3, which at least with respect to monomers M1 and also with respect to some of the monomers M2 and M3 can be obtained from bio-renewable sources, they allow for a significant reduction in the need of fossil carbon, in particular by at least 10%, especially at least 25% or even at least 40%, and up to 100%. The incorporation of bio-carbon and the reduction of fossil carbon can reduce the carbon footprint of the polymer latex.
  • the polymer latices are particularly useful as binders in waterborne architectural coatings, and have beneficial properties in both in waterborne primers and in water-borne top coat formulations and exterior and interior architectural paints.
  • bio-based monomer means that the respective monomer is at least partly produced from molecules, which are obtained from a bio-renewable resource, such as biomass.
  • Such molecules are characterized by a content of bio-carbon of at least 90 mol-%, preferably at least 95 mol-%, e.g. 100 mol- %, based on the total amount of carbon atoms in the respective molecule, such as 1- heptanol or isobutanol.
  • bio-carbon indicates that the carbon is of biological origin and comes from a biomaterial/renewable resources.
  • renewable sources and biorenewable sources are used synonymously and refer to sources of biological origin other than fossil sources.
  • the content in bio-carbon and the content in biomaterial are expressions that indicate the same value.
  • a material of renewable origin or biomaterial is an organic material wherein the carbon comes from the CO 2 fixed recently (on a human scale) by photosynthesis from the atmosphere.
  • a biomaterial Carbon of 100% natural origin
  • the isotopic 14 C is formed in the atmosphere and is then integrated via photosynthesis, according to a time scale of a few tens of years at most. The half-life of the 14 C is 5,730 years.
  • the materials coming from photosynthesis namely plants in general, necessarily have a maximum content in isotope 14 C.
  • the determination of the content of biomaterial or of bio-carbon can be carried out in accordance with the standards ASTM D 6866-12, the method B (ASTM D 6866-06) and ASTM D 7026 (ASTM D 7026-04).
  • the term “(meth)acryl” includes both acryl and methacryl groups.
  • the term “(meth)acrylate” includes acrylate and methacrylate and the term “(meth)acrylamide” includes acrylamide and methacrylamide.
  • waterborne coating composition and “waterborne adhesive composition”, respectively, mean a liquid aqueous coating or adhesive composition containing water as the continuous phase in an amount sufficient to achieve flowability.
  • pphm means parts per 100 monomers, i.e. parts by weight per 100 parts of monomers and corresponds to the relative amount in % by weight of a certain substance based on the total amount of monomers M.
  • ethoxylated and “polyethoxylated” are used synonymously and refer to compounds having an oligo- or polyoxyethylene group, which is formed by repeating units O-CH 2 CH 2 .
  • degree of ethoxylation relates to the number average of repeating units O-CH 2 CH 2 in these compounds.
  • non-ionic in the context of compounds, especially monomers, means that the respective compound does not bear any ionic functional group or any functional group, which can be converted by protonation or deprotonation into an ionic group.
  • C n -C m 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 "CrC n alkyl” denominates a group of linear or branched saturated hydrocarbon radicals having from 1 to n carbon atoms.
  • the term "C n /C m alkyl” denominates a mixture of two alkyl groups, one having n carbon atoms while the other having m carbon atoms.
  • C C 2 o alkyl denominate s a group of linear or branched saturated hydrocarbon radicals having from 1 to 20 carbon atoms
  • C C 4 alkyl denominate s a group of linear or branched saturated hydrocarbon radicals having from 1 to 4 carbon atoms
  • the C 5 -C 2 o alkyl denominate s a group of linear or branched saturated hydrocarbon radicals having from 5 to 20 carbon atoms.
  • alkyl examples include but are not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylpropyl (isopropyl), 1,1-dimethylethyl (tert-butyl), pentyl, 1- methylbutyl, 2-methylbutyl, 3 -methyl butyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1- dimethylpropyl, 1,2-dimethylpropyl, 1- methyl pentyl, 2-methylpentyl, 3 -methyl pentyl, 4- methylpentyl, 1,1 -di methyl butyl, 1,2-dimethylbutyl, 1,3 -di methyl butyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-eth
  • C 5 -C2 0 -cycloalkyl refers to an mono-, bi- or tricyclic cycloaliphatic radical which is unsubstituted or substituted by 1, 2, 3 or 4 methyl radicals, where the total number of carbon atoms of C 5 -C2o-cycloalkyl from 5 to 20.
  • 1 or 2 of the CH 2 groups may be replaced by non-adjacent oxygen ring atoms, resulting in heterocycloaliphatic radicals.
  • radicals include, but are not limited to oxolan-2-yl, oxolan-3-yl, oxan-2-yl, oxan-3-yl, oxan-4-yl, 1,3-dioxolan-2-yl, 1,3-dioxolan- 4-yl, 2,2-dimethyl-1,3-dioxolan-4-yl, 1,4-dioxan-2-yl, 1,3-dioxan-2-yl, 1,3-dioxan-4-yl, 1,3- dioxan-5-yl, 2,2-dimethyl-1,3-dioxan-4-yl, 2,2-dimethyl-1,3-dioxan-5-yl.
  • C 5 -C2 0 -cycloalkylmethyl refers to a C 5 -C2 0 -cycloalkyl radical as defined herein, which is bound via a methylene group.
  • the monomers M comprise a monomer M1 which is 1-heptyl acrylate.
  • 1-Heptyl acrylate is typically produced by esterification of acrylic acid with 1-heptanol or by transesterification of methyl acrylate or ethyl acrylate with 1-heptanol.
  • 1-Heptyl acrylate can be, at least with regard to its alkanol part, obtained from biological sources and thus allow for the reduction of fossil carbon in the polymer latices.
  • 1-Heptanol can be prepared from heptanal via catalytic hydrogenation as described e.g. in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag GmbH & Co.
  • Heptanal is preferably obtained, for instance, by pyrolysis of ricinoleic acid or its esters, which in turn are accessible from the seed oil of the castor plant, i.e. a biomass source.
  • 1-Heptanol prepared this way has a content of biocarbon of about 100 mol-% and, thus, allowing to produce 1-heptyl acrylate having a content of bio-carbon of at least 70 mol-%.
  • acrylic acid used for esterification may be obtained from fossil sources according to standard procedures.
  • acrylic acid may also be prepared from renewable raw materials, e.g. according to WO 2006/092272 or DE 10 2006 039 203 A or EP 2 922 580.
  • a particular embodiment of the invention relates to a polymer latex as defined herein, wherein at least the carbon atoms of the 1- heptyl groups in the monomer M1 are of biological origin, i.e. they are at least partly made of bio-carbon.
  • the 1-heptanol used for the production of the monomer M1 preferably has a content of bio-carbon of at least 90 mol-%, based on the total amount of carbon atoms in 1-heptanol.
  • This content is advantageously higher, in particular greater than or equal to 95 mol-%, preferably greater than or equal to 98 mol-% and advantageously equal to 100 mol-%.
  • acrylic acid may be produced from renewable materials.
  • acrylic acid and/or methacrylic acid produced from biomaterials is not available on large scale so far. Consequently, the monomer M1 has a content of bio-carbon of preferably at least 63 mol-%, in particular at least 69.5 mol-%, based on the total amount of carbon atoms in 1-heptyl acrylate.
  • the amount of carbon of biological origin of at least 10 mol-%, in particular at least 15 mol-% or at least 20 mol-% or higher, e.g. at least 30 mol-%, at least 40 mol-%, at least 50 mol-% or at least 60 mol- % or higher can be achieved.
  • the total amount of monomer M1 is from 5 to 90% by weight, in particular from 7.5 to 70% by weight or from 10 to 55% by weight, especially from 12 to 50% by weight, based on the total weight of the monomers M.
  • the monomers M forming the polymer of the latex may comprise one or more monomers M2 as defined above.
  • Suitable monomers M2 are selected from the group consisting of:
  • C 8 -C 20 -alkyl esters of acrylic acid including but are not limited to n-octyl acrylate, 2-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, isodecyl acrylate, 2-propylheptyl acrylate, lauryl acrylate, C 12 /C 14 -alkyl acrylate, C 12 -C 15 -alkyl acrylate, isotridecyl acrylate, C 17 -alkyl acrylate, C 16 /C 18 -alkyl acrylate and stearyl acrylate; C 5 -C 20 -alkyl esters of methacrylic acid, including but are not limited to n-pentyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, n-dec
  • Preferred monomers M2 are selected from the group consisting of ethyl acrylate, n- propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, 2-methylbutyl acrylate, isoamyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-octyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate and mixtures thereof.
  • the monomers M2 is selected from the group consisting of n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate and 2-octyl acrylate and mixtures thereof.
  • Isoamyl acrylate, 2-methylbutyl acrylate, isobutyl acrylate and/or 2-octyl acrylate may be produced from fossil sources or may at least be partly bio-based.
  • the carbon atoms of the isoamyl, 2- methylbutyl, isobutyl and/or 2-octyl group of isoamyl acrylate, 2-methylbutyl acrylate, isobutyl acrylate and 2-octyl acrylate, respectively are of biological origin, i. e. the monomers are obtained from esterification of acrylic acid, which may be bio-based or of fossil origin, with biobased isoamyl alcohol, 2-methylbutanol, isobutanol or 2-octanol, respectively.
  • the isobutyl group of isobutyl acrylate and/or the 2-octanol group of 2-octyl acrylate are of biological origin, i. e. the monomers are obtained from esterification of acrylic acid, which may be bio-based or of fossil origin, with biobased isobutanol or 2-octanol, respectively.
  • the monomers M2 comprise isobutyl acrylate, especially bio-based isobutyl acrylate.
  • the monomers M2 are isobutyl acrylate, especially bio-based isobutyl acrylate.
  • the monomers M2 may also be mixtures of isobutyl acrylate with at least one further C 2 -C 6 or C 8 -C 10 alkyl acrylate which is different from isobutyl acrylate, such as especially n-butyl acrylate, isoamyl acrylate, 2-methylbutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate, and in particular n-butyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate.
  • the amount of isobutyl acrylate is in the range of 1 to 70% by weight, in particular 10 to 60%, especially 20 to 50%, based on the total amount of monomers M.
  • the monomers M2 comprise n-butyl acrylate and especially is n-butyl acrylate.
  • n-butyl acrylate may be the sole monomer or a mixture of n-butyl acrylate with at least one further C 2 - C 6 or C 8 -C 10 alkyl acrylate which is different from n-butyl acrylate, such as especially isobutyl acrylate, isoamyl acrylate, 2-methylbutyl acrylate, 2-octyl acrylate and 2- ethylhexyl acrylate, and in particular isobutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate.
  • the amount of n-butyl acrylate is in the range of 1 to 60% by weight, in particular 10 to 50%, especially 15 to 40%, based on the total amount of monomers M.
  • Isobutyl acrylate, 2-methylbutyl acrylate, isopentyl acrylate and 2-octyl acrylate are typically produced by esterification of acrylic acid with isobutanol (2-methylpropan-1-ol), 2-methylbutanol, isopentanol (3-methylbutan-1-ol) or 2-octanol, respectively, or by transesterification of methyl acrylate or ethyl acrylate with isobutanol (2-methylpropan- l-ol), 2-methylbutan-1-ol, isopentanol (3-methylbutan-1-ol) or 2-octanol, respectively.
  • Isobutanol, 2-methylbutanol and isopentanol can be produced on large scale by fermentation from a variety of renewable feedstocks, including corn, wheat, sorghum, barley, and sugar cane, in particular from cellulose containing raw material and thus from biological sources or renewable raw materials, respectively.
  • fermentation may produce a mixture comprising different alkanols from which isobutanol, 2-methylbutan-1-ol and 3-methylbutan-1-ol can be separated by conventional techniques such as fractionated distillation.
  • the pure alcohols (purity > 90%) may be obtained or mixtures containing at least two alcohols selected from the group consisting of isobutanol, 2-methylbutan-1-ol and 3- methylbutan-1-ol in a total amount of at least 80%, in particular at least 90% can be obtained.
  • a mixture comprising at least 80% by weight of a mixture of 2- methyl butanol and 3-methyl butanol and up to 20% by weight of isobutanol may be used for esterification or trans-esterification.
  • the molar ratio of 3- methylbutanol to 2-methylbutan-1-ol may vary, e.g. from 1:10 to 10:1 and is in particular in the range of 1:1 to 10:1.
  • 2-Octanol can be produced by alkali-catalyzed thermal cleavage of ricinoleic acid with sebacic acid as a coproduct.
  • Castor oil which consists mainly of ricinoleic acid, is the main feedstock. Therefore, including these monomers M2 into the polymer latex significantly increases the amount of bio-carbon in the polymer latex. The incorporation of bio-carbon and the reduction of fossil carbon can reduce the carbon footprint of the polymer latex.
  • a particular embodiment of the invention relates to a polymer latex as defined herein, wherein at least the carbon atoms of the isobutyl group, the 2-methylbutyl group, the isoamyl group and the 2-octyl group, respectively, in the monomers M2, in particular at least the carbon atoms of the isobutyl group in the monomers M2 are of biological origin, i.e. they are at least partly made of bio-carbon.
  • the isobutanol, the 2-methylbutan-1-ol, the 3-methylbutanol and the 2- octanol, respectively, used for the production of the monomers M2 preferably have a content of bio-carbon of at least 90 mol-%, based on the total amount of carbon atoms in isobutanol, 2-methylpentanol, 3-methylbutanol and 2-octanol, respectively.
  • This content is advantageously higher, in particular greater than or equal to 95 mol-%, preferably greater than or equal to 98 mol-% and advantageously equal to 100 mol-%.
  • acrylic acid may be produced from renewable materials. However, acrylic acid produced from biomaterials is not available on large scale so far.
  • the monomers M2 have a content of bio-carbon of preferably at least 51 mol-%, in particular at least 54 mol-% and especially at least 57 mol-%, based on the total amount of carbon atoms in isobutyl acrylate, 2-methylbutyl acrylate, isopentyl acrylate and 2- octyl acrylate, respectively.
  • monomers M2 which are at least partly of biological origin, the demand of fossil carbon in the polymer latex can be significantly reduced.
  • the amount of carbon of biological origin of at least 5 mol-%, in particular at least 10 mol-% or at least 15 mol-% or higher, e.g. 20 mol-% or 30 mol-% or higher can be achieved.
  • the total amount of monomers M2 is from 0 to 70% by weight, in particular from 0 to 60% by weight or 1 to 60% by weight, especially from 1 to 50% by weight or from 5 to 50% by weight, based on the total weight of the monomers M.
  • the monomers M comprise, based on the total amount of monomers M, 15 to 80% by weight, preferably 20 to 70% by weight and in particular 25 to 60% by weight of the monomer M1;
  • the monomers M comprise, based on the total amount of monomers M,
  • the monomers M2 are selected in particular from isobutyl acrylate and mixtures of isobutyl acrylate with at least one of n-butyl acrylate, 2-octyl acrylate and 2- ethylhexyl acrylate, the carbon atoms of isobutyl acrylate and, if present, 2-octyl acrylate preferably being at least partly of biological origin; and
  • the monomers M comprise, based on the total amount of monomers M,
  • the monomers M2 are selected in particular from n-butyl acrylate and mixtures of n-butyl acrylate with at least one of isobutyl acrylate, 2-octyl acrylate and 2- ethylhexyl acrylate, the carbon atoms of isobutyl acrylate and 2-octyl acrylate, if present, preferably being at least partly of biological origin; and
  • the monomers M forming the polymer of the latex may comprise one or more monomers M3 as defined above.
  • Suitable monomers M3 are selected from the group consisting of:
  • Ci-C 4 -alkyl esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, isobutyl methacrylate and tert-butyl methacrylate; tert-butyl acrylate;
  • C 5 -C2o-cycloalkyl esters of (meth)acrylic acid including but are not limited to cyclopentyl acrylate, cyclopentyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, norbornyl acrylate, norbornyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 1,3-dioxan-5-yl-acrylate, 1,3-dioxan-5-yl-methacrylate, 2,2- dimethyl-1,3-dioxan-5-yl-acrylate, 2,2-dimethyl-1,3-dioxan-5-yl-methacrylate;
  • C 5 -C2o-cycloalkylmethyl esters of (meth)acrylic acid including but are not limited to cyclopentyl methylacrylate, cyclopentyl methyl methacrylate, cyclohexyl methyl acrylate, cyclohexyl methyl methacrylate, 1,3-dioxolan-4-yl-methyl acrylate, 1,3- dioxolan-4-ylmethyl methacrylate, 2,2-dimethyl-1,3-dioxolan-4-ylmethyl acrylate, 2,2-dimethyl-1,3-dioxolan-4-ylmethyl methacrylate, oxolan-2-yl-methyl acrylate (tetrahydrofurfuryl acrylate) and oxolan-2-yl-methyl methacrylate (tetra hyd rofu rf u ry I m ethac ry I ate); methylene-gamma-buty
  • monomers M3 are selected from the group consisting of:
  • CrC 4 -alkyl esters of methacrylic acid in particular methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and tert-butyl methacrylate; tert-butyl acrylate; cyclopentyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate; alpha-methylene-gamma-butyrolactone; styrene; and mixtures thereof.
  • monomers M3 are particularly selected from the group consisting of: methyl methacrylate, n-butyl methacrylate; tert-butyl acrylate; cyclopentyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate; alpha-methylene-gamma-butyrolactone; styrene; and mixtures thereof.
  • the monomers M3 comprise methyl methacrylate in an amount of at least 50% by weight, in particular at least 80% by weight or 100% by weight, based on the total amount of monomers M3 in the monomers M.
  • the monomer M3 is selected from the group consisting of methyl methacrylate and combinations of methyl methacrylate with at least one further monomer M3 selected from n-butyl methacrylate, tert-butyl acrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, alpha-methylene- gamma-butyrolactone and styrene, in particular selected from n-butyl methacrylate, tert-butyl acrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate and styrene.
  • the total amount of monomers M3 is from 5 to 70% by weight, in particular from 15 to 70% by weight or from 25 to 65% by weight, especially from 35 to 62% by weight, based on the total weight of the monomers M.
  • the total amount of monomers M1 and M2 is preferably in the range from 10 to 90% by weight, in particular in the range from 20 to 80% by weight, especially in the range of 25 to 70% by weight, based on the total amount of ethylenically unsaturated monomers M.
  • the total amount of monomers M1, M2 and M3 is at least 90% by weight, in particular at least 94% by weight, especially at least 97% by weight, based on the total amount of ethylenically unsaturated monomers M.
  • the weight ratio of M1 to M3 is generally in the range of 1:10 to 5:1, in particular 1:6 to 3:1, preferably in the range of 1:5 to 2:1, especially in the range of 1:4 to 1.5:1.
  • the weight ratio of M1 to M2 is generally in the range of 1:10 to 2:1, in particular 1:4 to 1.5:1, preferably in the range of 1:3 to 1:1.
  • the monomers M may further comprise at least one monomer M4, which is selected from monoethylenically unsaturated monomers having an acidic group.
  • Suitable monomers M4 include, but are not limited to monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, such as acrylic acid, methacrylic acid, crotonic acid, 2-ethylpropenoic acid, 2-propylpropenoic acid, 2-acryloxyacetic acid and 2-methacryloxyacetic acid; monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, such as itaconic acid, citraconic acid and fumaric acid; semi-esters of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, with C C 4 alkanols, such as methanol or ethanol, such as semiesters of itaconic acid, citraconic acid, maleic acid or fumaric acid with methanol or ethanol; monoethylenically unsaturated sulfonic acids, such as vinylsulfonic acid, allylsulfonic acid, s
  • the aforementioned monomers M4 can be present in their acidic form or in the form of their salts, in particular in the form of their alkali metal salts or ammonium salts.
  • monoethylenically unsaturated monocarboxylic acids preference is given to monoethylenically unsaturated dicarboxylic acids and monoethylenically unsaturated sulfonic acids and the salts thereof, in particular the alkali metal salts and ammonium salts.
  • monoethylenically unsaturated monocarboxylic acids preference is given to monoethylenically unsaturated dicarboxylic acids and monoethylenically unsaturated sulfonic acids and the salts thereof, in particular the alkali metal salts and ammonium salts.
  • monoethylenically unsaturated monocarboxylic acids and monoethylenically unsaturated dicarboxylic acids and the salts thereof in particular the alkali metal salts and ammonium salts, in particular to acrylic acid, methacrylic acid, itaconic acid, the salts thereof, in particular the alkali metal salts and ammonium salts and combinations of the aforementioned monomers.
  • the monomer M4 comprises acrylic acid or a salt thereof, in particular an alkali metal salt or an ammonium salt.
  • the monomer M4 is acrylic acid or a salt thereof, in particular an alkali metal salt or an ammonium salt, or a mixture of acrylic acid and methacrylic acid or salts thereof, in particular the alkali metal salts or ammonium salts.
  • the monomer M4 comprises methacrylic acid or a salt thereof, in particular an alkali metal salt or an ammonium salt.
  • the monomer M4 is methacrylic acid or a salt thereof, in particular an alkali metal salt or an ammonium salt.
  • the total amount of monomers M4 is from 0.05 to 5% by weight or from 0.1 to 4% by weight, in particular from 0.05 to 3.5% by weight or from 0.1 to 3% by weight, especially from 0.2 to 2.5% by weight or from 0.5 to 2% by weight or from 0.5 to 1.5% by weight, based on the total weight of the monomers M.
  • the monomers M may further comprise at least one monoethylenically unsaturated, non-ionic monomer M5, which has a solubility in deionized water at 20°C and 1 bar of at least 60 g/L.
  • Suitable monomer M5 is selected from the group consisting of non-ionic monoethylenically unsaturated monomers which have a functional group selected from the group consisting of hydroxyalkyl groups, in particular hydroxy-C 2 -C 4 -alkyl group, a primary carboxamide group, urea groups, keto groups and combinations thereof.
  • the total amount of monomers M5 will usually not exceed 10% by weight, in particular 7% by weight, based on the total amount of monomers M.
  • the total amount of monomers M5 is usually 0 to 9.95% by weight, if present, from 0.05 to 9.95% by weight, in particular 0.1 to 7% by weight, especially from 0.1 to 5% by weight or 0.1 to 4% by weight or 0.5 to 3% by weight or 1 to 3% by weight, based on the total weight of the monomers M.
  • monomers M5 having a carboxamide group examples include, but are not limited to primary amides of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, such as acrylamide and methacrylamide, and Ci-C 4 -alkylamides of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, 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.
  • primary amides of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms such as acrylamide and methacrylamide
  • monomer M5a is selected from acrylamide and methacrylamide, and especially is arylamide.
  • monomers M5 having a urea group are the Ci-C 4 -alkyl esters of acrylic acid or methacrylic acid and the N-C C 4 -alkyl amides of acrylic acid or methacrylic acid, where the C r C 4 -alkyl group bears an urea group or a 2- oxoimidazolin group such as 2-(2-oxo-imidazolidin-1-yl)ethyl acrylate, 2-(2-oxo- imidazolidin-1-yl)ethyl methacrylate, which are also termed 2-ureido acrylate and 2-ureido methacrylate, respectively, N-(2-acryloxyethyl)urea, N-(2-methacryloxyethyl)urea, N-(2-(2-oxo-imidazo
  • monomers M5 having a keto group examples include the C 2 -C 8 -oxoalkyl esters of acrylic acid or methacrylic acid and the N-C 2 -C 8 -oxoalkyl amides of acrylic acid or methacrylic acid, such as diacetoneacrylamide (DAAM), and diacetonemethacrylamide, and
  • DAAM diacetoneacrylamide
  • acetoacetoxy group such as acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate and 2-(acetoacetoxy)ethyl methacrylate.
  • the monomer M5 comprises acrylamide or metharylamide, and in particular comprises acrylamide.
  • the monomer M4 is acrylamide or metharylamide, and in particular is acrylamide.
  • the monomers M comprise or consist of: i. 5 to 90% by weight, in particular 7.5 to 70% by weight or 10 to 55% by weight, especially 12 to 50% by weight, based on the total amount of monomers M, of 1- heptyl acrylate as monomer M1; ii. 0 to 70% by weight, in particular 0 to 60% by weight or 1 to 60% by weight, especially 1 to 50% by weight or 5 to 50% by weight, based on the total amount of monomers M, of at least one monomer M2, which comprises or is isobutyl acrylate; iii.
  • 0.05 to 9.95% by weight in particular 0.1 to 7% by weight, especially 0.1 to 5% by weight or 0.1 to 4% by weight or 0.5 to 3% by weight or 1 to 3% by weight, based on the total weight of the monomers M, of one or more non-ionic monomers M5 having a solubility in deionized water at 20°C and 1 bar of at least 60 g/L, or i. 5 to 90% by weight, in particular 7.5 to 70% by weight or 10 to 55% by weight, especially 12 to 50% by weight, based on the total amount of monomers M, of 1- heptyl acrylate as monomer M1; ii.
  • 0 to 70% by weight in particular 0 to 60% by weight or 1 to 60% by weight, especially 1 to 50% by weight or 5 to 50% by weight, based on the total amount of monomers M, of at least one monomer M2, which comprises or is n-butyl acrylate; iii. 5 to 70% by weight, in particular 15 to 70% by weight or 25 to 65% by weight, especially 35 to 62% by weight, based on the total amount of monomers M, of at least one monomer M3, which comprises or is methyl methacrylate; iv.
  • 0.05 to 9.95% by weight in particular 0.1 to 7% by weight, especially 0.1 to 5% by weight or 0.1 to 4% by weight or 0.5 to 3% by weight or 1 to 3% by weight, based on the total weight of the monomers M, of one or more non-ionic monomers M5 having a solubility in deionized water at 20°C and 1 bar of at least 60 g/L, where the total amount of monomers M1 and M3 is in the range from 10 to 98% by weight, in particular in the range from 22.5 to 85% by weight, especially in the range of 35 to 70% by weight, based on the total amount of ethylenically unsaturated monomers M, and where the total amount of monomers M1, M2 and M3 is at least 90% by weight, in particular at least 94% by weight, especially at least 97% by weight, based on the total amount of ethylenically unsaturated monomers M.
  • the monomers M comprise or consist of: i. 15 to 79,95% by weight, in particular 20 to 69.85% by weight, especially 25 to 59.4% by weight, based on the total amount of monomers M, of 1-heptyl acrylate as monomer M1; ii. 20 to 70% by weight, in particular 30 to 70% by weight, especially 40 to 65% by weight, based on the total amount of monomers M, of monomer M3, which comprises or is methyl methacrylate; iii.
  • the monomers M comprise or consist of: i. 15 to 79.95% by weight, in particular 20 to 69.85% by weight, especially 25 to 59.4% by weight, based on the total amount of monomers M, of 1-heptyl acrylate as monomer M1, wherein at least the carbon atoms of the 1-heptyl groups in 1- heptyl acrylate are of biological origin, particularly the content of bio-carbon of 1- heptyl acrylate is at least 63 mol-%, in particular at least 69.5 mol-%; ii.
  • monomers M2 which are a mixture of isobutyl acrylate with at least one of n-butyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate, wherein at least the carbon atoms of the isobutyl groups in isobutyl acrylate are of biological origin, particularly the content of biocarbon of isobutyl acrylate is at least 54 mol-%, in particular at least 57 mol-%; iii.
  • the monomers M may comprise one or more further monomers, which are different from the aforementioned monomers M.
  • Suitable monomers M which are different from the monomers M1, M2, M3, M4 and M5 include, but are not limited to monomers M6, which are selected from monoethylenically unsaturated non-ionic monomers having a silane functional group or an epoxy group; monomers M7, which are selected from multiethylenically unsaturated monomers, i.e. monomers having at least two non-conjugated ethylenically unsaturated double bounds; monomers M8, which are selected from monoethylenically unsaturated copolymerizable UV-initiators.
  • Suitable monomers M6 include monoethylenically unsaturated silane functional monomers (monomers M6a), e.g. monomers which in addition to an ethylenically unsaturated double bond bear at least one mono-, di- and/or tri-CrC 4 -alkoxysilane group, such as vinyl trimethoxysilane, vinyl triethoxysilane, methacryloxymethyl tri methoxysilane, methacryloxymethyl triethoxysilane, methacryloxypropyl tri methoxysilane, methacryloxypropyl triethoxysilane, methacryloxyethyl trimethoxysilane, methacryloxyethyl triethoxysilane, and mixtures thereof.
  • monomers M6a monoe.g. monomers which in addition to an ethylenically unsaturated double bond bear at least one mono-, di- and/or tri-CrC 4 -alkoxysilane group,
  • silan functional monomers M6a if present, will usually not exceed 1% by weight, and frequently be in the range of 0.01 to 1% by weight, preferably in the range of 0.05 to 0.7% by weight, based on the total amount of ethylenically unsaturated monomers M.
  • Suitable monomers M6 also include monoethylenically unsaturated monomers bearing at least one epoxy group (monomers M6b), in particular a glycidyl group such as glycidyl acrylate, glycidyl methacrylate, 2-glycidyloxyethyl acrylate and 2-glycidyloxyethyl methacrylate.
  • the amount of monomers M6b, if present, will usually not exceed 2% by weight, and frequently be in the range of 0.01 to 2% by weight, preferably in the range of 0.05 to 1% by weight, based on the total amount of ethylenica I ly unsaturated monomers M.
  • the monomers M may also include mu Itiethylenically unsaturated monomers (monomers M7), i.e. monomers having at least two non-conjugated ethylenica I ly unsaturated double bounds.
  • the amounts of said monomers M7 will generally not exceed 1% by weight, and frequently be in the range of 0 to 1% by weight, especially 0 to 0.5% by weight, based on the total amount of ethylenically unsaturated monomers M.
  • mu Itiethylenically unsaturated monomers M7 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), 1,6-hexanediol and 1,2-cyclohexanediol; monoesters of monoethylenically unsaturated C 3 -C 6 monocarboxylic acids with monoethylenically unsaturated aliphatic or cycloalipha
  • Polymerized monoethylenically unsaturated copolymerizable UV-initiators M8 result in a crosslinking of the polymer chain upon exposure to sunlight.
  • Monomers M8 bear an ethylenically unsaturated double bond, in particular an acrylate or methacrylate group and a moiety that is decomposed by UV radiation whereby a radical is formed.
  • groups are typically benzophenone groups, acetophenone groups, benzoin groups or carbonate groups attached to a phenyl ring.
  • Such compounds are disclosed e.g. in EP 346734, EP 377199, DE 4037079, DE 3844444, EP 1213 and US2015/0152297.
  • the amounts of said monomers M8 will generally not exceed 1% by weight, and, if present, are typically present in the range of 0.01 to 1% by weight,, especially 0.02 to 0.5% by weight, based on the total amount of ethylenically unsaturated monomers M .
  • the monomers M consist of: i.
  • monomers M 0.05 to 5% by weight, in particular 0.1 to 4% by weight, especially 0.5 to 3% by weight, based on the total amount of monomers M, of one or more monoethylenically unsaturated monomers M4, which is selected from acrylic acid, methacrylic acid, itaconic acid and combinations thereof; iv.
  • the total amount of monomers M1 and M3 is in the range from 15 to 90% by weight, in particular in the range from 25 to 80% by weight, especially in the range of 35 to 70% by weight, based on the total amount of ethylenically unsaturated monomers M, and where the total amount of monomers M1, M2 and M3 is at least 90% by weight, in particular at least 94% by weight, especially at least 97% by weight, based on the total amount of ethylenically unsaturated monomers M; or i.
  • monomers M2 which are a mixture of isobutyl acrylate with at least one of n-butyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate, wherein at least the carbon atoms of the isobutyl groups in isobutyl acrylate are of biological origin, particularly the content of biocarbon of isobutyl acrylate is at least 54 mol-%, in particular at least 57 mol-%; iii.
  • the total amount of monomers M1 and M3 is in the range from 15 to 90% by weight, in particular in the range from 25 to 80% by weight, especially in the range of 35 to 70% by weight, based on the total amount of ethylenically unsaturated monomers M, and where the total amount of monomers M1, M2 and M3 is at least 90% by weight, in particular at least 94% by weight, especially at least 97% by weight, based on the total amount of ethylenically unsaturated monomers M; or i.
  • the total amount of monomers M1 and M3 is in the range from 15 to 90% by weight, in particular in the range from 25 to 80% by weight, especially in the range of 35 to 70% by weight, based on the total amount of ethylenically unsaturated monomers M, and where the total amount of monomers M1, M2 and M3 is at least 90% by weight, in particular at least 94% by weight, especially at least 97% by weight, based on the total amount of ethylenically unsaturated monomers M.
  • the particles of the copolymer contained in the polymer latex have a Z-average particle diameter, as determined by quasi-elastic light scattering (QELS), in the range from 30 to 500 nm, in particular in the range from 40 to 350 nm.
  • the particle size distribution of the copolymer particles contained in the polymer latex may be monomodal or almost monomodal, which means that the distribution function of the particle size has a single maximum and no particular shoulder.
  • the particle size distribution of the copolymer particles contained in the polymer latex may also be polymodal or almost polymodal, which means that the distribution function of the particle size has at least two distinct maxima or at last one maximum and at least a pronounced shoulder.
  • the size of the particles as well as the distribution of particle size is determined by quasielastic light scattering (QELS), also known as dynamic light scattering (DLS).
  • QELS quasielastic light scattering
  • DLS dynamic light scattering
  • HPPS High-Performance Particle Sizer
  • a sample of the aqueous polymer latex will be diluted and the dilution will be analyzed.
  • 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.
  • 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.
  • 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 temperature 20.0°C measurement time 120 seconds (6 cycles each of 20 s); scattering angle 173°; wavelength laser 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.
  • the hydrodynamic particle diameter can also be determined by Hydrodynamic Chromatography fractionation (HDC), as for example described by H. Wiese, "Characterization of Aqueous Polymer Dispersions” in Polymer Dispersions and Their Industrial Applications (Wiley-VCH, 2002), pp. 41-73.
  • HDC Hydrodynamic Chromatography fractionation
  • the particles of the copolymer contained in the polymer latex have a Z-average particle diameter, as determined by QELS, in the range from 30 to 200 nm, in particular in the range from 40 to 150 nm.
  • the particle size distribution of the copolymer particles contained in the polymer latex is in particular monomodal or almost monomodal, which means that the distribution function of the particle size has a single maximum.
  • the copolymer contained in the polymer particles may form a single phase or it may form different phases, if the polymer particles contain different copolymers, which differ with regard to their monomer composition.
  • the polymer particles contained in the aqueous polymer latex of the present invention comprise a polymer phase, which has a glass transition temperature Tg which does not exceed 50°C and is in particular at most 40°C, especially at most 30°C, preferably in the range from -40 to +50°C, more preferably in the range from -25 to +40°C and especially in the range from -20 to +30°C.
  • the glass transition temperatures as referred to herein are the actual glass transition temperatures.
  • the actual glass transition temperature can be determined experimentally by the differential scanning calorimetry (DSC) method according to ISO 11357-2:2013, preferably with sample preparation according to ISO 16805:2003.
  • the actual glass transition temperature depends from the monomer compositions forming the polymer, and a theoretical glass transition temperature can be calculated from the monomer composition used in the emulsion polymerization.
  • the theoretical glass transition temperatures are usually calculated from the monomer composition by the Fox equation:
  • x a , x b , .... x n are the mass fractions of the monomers a, b, .... n and Tg a , Tg b , .... Tg n are the actual glass transition temperatures in Kelvin of the homopolymers synthesized from only one of the monomers 1, 2, .... n at a time.
  • the Fox equation is described by T. G. Fox in Bull. Am. Phys. Soc. 1956, 1, page 123 and as well as in Ullmann's Encyclopadie der ischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], vol. 19, p. 18, 4th ed., Verlag Chemie, Weinheim, 1980.
  • the theoretical glass temperature Tg 1 calculated according to Fox as described herein and the experimentally determined glass transition temperature as described herein are similar or even same and do not deviate from each other by more than 5 K, in particular they deviate not more than 2 K. Accordingly, both the actual and the theoretical glass transition temperatures of the polymer phases (1) and (2) can be adjusted by choosing proper monomers Ma, Mb ... Mn and their mass fractions x a , x b , .... x n in the monomer composition so to arrive at the desired glass transition temperature Tg(1) and Tg(2), respectively. It is common knowledge for a skilled person to choose the proper amounts of monomers Ma, Mb ... Mn for obtaining a copolymer and/or copolymer phase with the desired glass transition temperature.
  • the copolymers formed by the monomers M and contained in the polymer latices of the present invention are film forming, which means that upon drying of the polymer latex the particles of the copolymer forms a film.
  • the aqueous copolymer latexes of the present invention have a minimum film forming temperature (MFT) of not more than 50°C, not more than 40°C.
  • MFT film forming temperature
  • the MFFT is defined as the lowest temperature at which a polymer latex applied to a surface of a substrate still forms a closed, uniform and crack-free coating after drying (see Ullmann's Encyclopadie der ischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], vol.
  • the minimum film forming temperature correlates with the lowest glass transition temperature of the copolymer but may be typically somewhat lower, e.g. 1 to 5 K lower than the actual glass transition temperature Tg of the polymer P.
  • the MFFT cannot be lower than 0°C, because the latex will typically freeze.
  • the aqueous polymer latices of the present invention have a pH of at least pH 3, e.g. in the range of pH 3 to pH 11.5.
  • the aqueous polymer dispersions of the present invention generally have solids contents in the range of 30 to 75% by weight, in particular in the range of 40 to 65% by weight, preferably in the range of 45 to 60% by weight.
  • the solids content describes the proportion of nonvolatile fractions.
  • the solids content of a dispersion is determined by means of a balance with infrared moisture analysis. In this determination, a quantity of polymer dispersion is introduced into the instrument, heated to 140°C and subsequently held at that temperature.
  • the ratio of weight after drying to original mass introduced gives the solids content of the polymer dispersion.
  • the total solids content of the formulation is determined arithmetically from the amounts of the substances added and from their solids contents and concentrations.
  • the polymer dispersions may contain a crosslinking agent for achieving postcrosslinking of the polymer latex particles, if the polymer in the polymer latex has functional groups which are complementary to the functional groups of the crosslinking agent.
  • a crosslinking agent for achieving postcrosslinking of the polymer latex particles, if the polymer in the polymer latex has functional groups which are complementary to the functional groups of the crosslinking agent.
  • the term "complementary" is understood that the functional groups of the latex and the functional groups of the crosslinking agent are susceptible to undergo a chemical reaction which forms a chemical bond between the atoms of the respective functional groups.
  • the crosslinking agent has at least two functional groups complementary to the functional groups of the polymer of the polymer latex. Examples of suitable crosslinking agents are described below.
  • the aqueous polymer dispersions of the present invention may contain further ingredients conventionally present in aqueous polymer dispersions.
  • these further ingredients are, for example, surface active compounds, such as emulsifiers und protective colloids, in particular those used in the production of the polymer latex, further defoamers and the like.
  • Further ingredients may also be acids, bases, buffers, decomposition products from the polymerization reaction, deodorizing compounds, and chain transfer agents.
  • the polymer latex may contain biozides for avoiding microbial spoilage. The amount of the respective individual component will typically not exceed 1.5 wt%, based on the total weight of the polymer dispersion. The total amount of these stated components will typically not exceed 5 wt%, based on the total weight of the polymer latex.
  • the amount of volatile organic matter i.e. the content of organic compounds with boiling points up to 250°C under standard conditions (101,325 kPa) as determined by ISO 17895:2005 via gas-chromatography is less than 0.5% by weight, in particular less than 0.2% by weight, based on the total weight of the polymer latex.
  • the aqueous polymer latex also contains an aqueous phase, wherein the polymer particles of the polymer latex are dispersed.
  • the aqueous phase also termed serum, consists essentially of water and any water-soluble further ingredients. The total concentration of any further ingredient will typically not exceed 10 wt%, in particular 8% by weight, based on the total weight of the aqueous phase.
  • the aqueous polymer latex of the present invention can be prepared by any method for preparing an aqueous dispersion of a polymer made of polymerized monomers M.
  • aqueous polymer latices of the present invention are prepared by an aqueous emulsion polymerization, in particular by a free radical aqueous emulsion polymerization of the monomers M.
  • free radical aqueous emulsion polymerization means that the polymerization of the monomers M is initiated by radicals formed by the decay of a polymerization initiator, whereby free radicals are formed in the polymerization mixture. It is therefore also termed "radically initiated emulsion polymerization".
  • the radically initiated aqueous emulsion polymerization is typically carried out by emulsifying the ethylenically unsaturated monomers in the aqueous medium which forms the aqueous phase, typically by use of surface active compounds, such as emulsifiers and/or protective colloids, and polymerizing this system using at least one initiator which decays by formation of radicals and thereby initiates the chain growth addition polymerization of the ethylenically unsaturated monomers M.
  • surface active compounds such as emulsifiers and/or protective colloids
  • the process shall, for the purposes of the present specification, also encompass the seed, staged, one-shot, and gradient regimes which are familiar to the skilled person.
  • the free-radically initiated aqueous emulsion polymerization is triggered by means of a free-radical polymerization initiator (free-radical initiator).
  • free-radical initiator may, in principle, be peroxides or azo compounds.
  • redox initiator systems are also useful.
  • Peroxides used may, in principle, 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, or organic peroxides such as alkyl hydroperoxides, for example tert-butyl hydroperoxide, 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 salts of peroxodisulfuric acid, for example the mono- and disodium, -potassium or ammonium salts
  • organic peroxides such as alkyl hydroper
  • Azo compounds used are essentially 2,2'-azobis(isobutyronitri le), 2,2'-azobis(2,4-dimethylvaleronitrile) and 2,2'-azobis(amidinopropyl) dihydrochloride (AIBA, corresponds to V-50 from Wako Chemicals).
  • Suitable oxidizing agents for redox initiator systems are essentially the peroxides specified above.
  • Corresponding reducing agents which may be used 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, alkali metal metabisulfites, for example potassium and/or sodium metabisulfite, formaldehydesulfoxylates, for example potassium and/or sodium formaldehydesulfoxylate, 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(ll) sulfate, iron(ll) ammonium sulfate, iron(ll) phosphate, ene diols such as dihydroxymaleic acid, benzoin and/or ascorbic acid, and reducing saccharides such as sorbose, glucose, fruct
  • Preferred free-radical initiators are inorganic peroxides, especially peroxodisulfates.
  • the amount of the free-radical initiator used based on the total amount of monomers M, is 0.05 to 2 pphm, preferably 0.1 to 1 pphm, based on the total amount of monomers M.
  • the amount of free-radical initiator required for the emulsion polymerization of monomers M can be initially charged in the polymerization vessel completely. However, it is also possible to charge none of or merely a portion of the free-radical initiator, for example not more than 30% by weight, especially not more than 20% by weight, based on the total amount of the free-radical initiator and then to add any remaining amount of free-radical initiator to the free-radical polymerization reaction under polymerization conditions. Preferably, at least 70%, in particular at least 80%, especially at least 90% or the total amount of the polymerization initiator are fed to the free-radical polymerization reaction under polymerization conditions. Feeding of the monomers M may be done according to the consumption, batch-wise in one or more portions or continuously with constant or varying flow rates during the free-radical emulsion polymerization of the monomers M.
  • polymerization conditions is 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 free-radical initiator used.
  • the type and amount of the free-radical 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 radical emulsion polymerization of the monomers M is performed by a so-called feed process (also termed monomer feed method), which means that at least 80%, in particular at least 90% or the total amount of the monomers M to be polymerized are metered to the polymerization reaction under polymerization conditions during a metering period P. Addition may be done in portions and preferably continuously with constant or varying feed rate.
  • the duration of the period P may depend from the production equipment and may vary from e.g. 20 minutes to 12 h. Frequently, the duration of the period P will be in the range from 0.5 h to 8 h, especially from 1 h to 6 h.
  • the total duration of all steps is typically in the above ranges.
  • the duration of the individual steps is typically shorter.
  • at least 70%, in particular at least 80%, especially at least 90% or the total amount of the polymerization initiator is introduced into emulsion polymerization in parallel to the addition of the monomers.
  • the aqueous radical emulsion polymerization is usually performed in the presence of one or more suitable surfactants.
  • surfactants typically comprise emulsifiers and provide micelles, in which the polymerization occurs, and which serve to stabilize the monomer droplets during aqueous emulsion polymerization and also growing polymer particles.
  • the surfactants used in the emulsion polymerization are usually not separated from the polymer dispersion, but remain in the aqueous polymer dispersion obtainable by the emulsion polymerization of the monomers M.
  • 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 typically 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
  • the salts, especially the alkali metal and ammonium salts, of alkylsulfonic acids especially of C 8 -C 22 -a I kylsu Ifonic acids
  • anionic emulsifiers which bear a phosphate or phosphonate group, include, but are not limited to the following salts are 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
  • Anionic emulsifiers may also comprise emulsifiers, which have a polymerizable double bond, e.g. the emulsifiers of the formulae (I) to (IV) and the salts thereof, in particular the alkalimetal salts or ammonium salts thereof:
  • R 1 is H, C 1 -C 2 o-alkyl, C 5 -C 10 -cycloalkyl, phenyl optionally substituted with CrC 20 -alkyl, R 2 and R 2 ' are both H or together are O, R 3 and R 4 are H or methyl, m is 0 or 1, n is an integer from 1 - 100 and X is SO 3 _ , O-SO 3 _ , O-HPO 3 _ or O-PO 3 2- .
  • R is H, Ci-C 20 -alkyl, C 5 -C 10 -cycloalkyl, phenyl optionally substituted with Ci-C 20 -alkyl, k is 0 or 1 and X is SO 3 _ , O-SO 3 _ , O-HPO 3 _ or O-PO 3 2- .
  • R 1 is H, C 1 -C 2 o-alkyl, 0-Ci-C 2 o-alkyl, C 5 -Ci 0 -cycloalkyl, O-C 5 -C 10 -cycloalkyl, O-phenyl optionally substituted with CrC 20 -alkyl, n is an integer from 1 - 100 and Y is SO 3 _ , HPO 3 _ or PO 3 2- .
  • R 1 is H, CrC 20 -alkyl or 1 -phenylethyl
  • R 2 is H, CrC 20 -alkyl or 1-phenylethyl
  • A is C 2 -C 4 -alkanediyl, such as 1,2-ethanediyl, 1,2-propanediyl, 1,2-butanediyl or 1,4- butanediyl
  • n is an integer from 1 - 100
  • Y is SO 3 _ , HPO 3 _ or PO 3 2- .
  • copolymerizable emulsifiers of the formula (I) are referred to as sulfate esters or phosphate esters of polyethylene glycol monoacrylates. Particular embodiments of the copolymerizable emulsifiers of the formula (I) may likewise also be referred to as phosphonate esters of polyethylene glycol monoacrylates, or allyl ether sulfates.
  • Commercially available co-polymerizable emulsifiers of the formula (I) are Maxemul® emulsifiers, Sipomer® PAM emulsifiers, Latemul® PD, and ADEKA Reasoap® PP-70.
  • copolymerizable emulsifiers of the formula (II) are also referred to as alkyl allyl sulfosuccinates.
  • Commercially available copolymerizable emulsifiers of the formula (II) is Trem® LF40.
  • copolymerizable emulsifiers of the formula (III) are also referred to as branched unsaturated.
  • Commercially available copolymerizable emulsifiers of the formula (III) are Adeka® Reasoap emulsifiers and Hitenol® KH.
  • copolymerizable emulsifiers of the formula (IV) are also referred to as polyoxyethylene alkyl phenyl ether sulfate and polyoxyethylene mono- or distyrylphenyl ether sulfate.
  • Commercially available copolymerizable emulsifiers of the formula (IV) are Hitenol® BC and Hitenol® AR emulsifiers.
  • 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.
  • Preferred anionic surfactants are anionic emulsifiers which are selected from the following groups, including mixtures thereof: the salts, especially the alkali metal and ammonium salts, of alkyl sulfates, especially of C 8 -C 22 -a I kyl sulfates, the salts, especially the alkali metal salts, of sulfuric monoesters of ethoxylated alkanols, especially of sulfuric monoesters of ethoxylated C 8 -C 2 2-alkanols, preferably having an ethoxylation level (EO 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 -C2 2 -alkylbenzenesulfonic acids, and of mono- or
  • anionic emulsifiers which are selected from the following groups including mixtures thereof: the salts, especially the alkali metal and ammonium salts, of alkyl sulfates, especially of C 8 -C 22 -a I kyl sulfates, the salts, especially the alkali metal salts, of sulfuric monoesters of ethoxylated alkanols, especially of sulfuric monoesters of ethoxylated C 8 -C 2 2-alkanols, preferably having an ethoxylation level (EO level) in the range from 2 to 40, of mono- or disulfonated, alkyl-substituted diphenyl ethers, for example of bisfphenylsulfonic acid) ethers bearing a C 4 -C 24 -alkyl group on one or both aromatic rings polymerizable emulsifiers of the formula (III), where Y is SO 3 _ .
  • the salts especially the alkali metal and ammoni
  • 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 alkyl radical C 8 -C 30 having a mean ethoxylation level of 5 to 100 and, among these, particular preference to those having a linear C 12 -C 2 o 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 will usually comprise not more than 30% by weight, especially not more than 20% 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.
  • Combinations of at least one anionic surfactant and at least non-ionic surfactant may also be used.
  • the weight ratio of the total amount of anionic surfactant to the total amount of non-ionic surfactant is in the range of 99:1 to 70:30, in particular 98:2 to 75:25, especially in the range 95:5 to 80:20.
  • 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 0.3 to 4.5% by weight, based on the monomers M to be polymerized.
  • the surfactant will be used in such an amount that the amount of surfactant is usually in the range from 0.2 to 5% by weight, especially in the range from 0.3 to 4.5% by weight, based on the total amount of monomers polymerized in the respective steps.
  • the major portion i.e. at least 80% of the surfactant used, is added to the emulsion polymerization in parallel to the addition of the monomers.
  • the monomers are added as an aqueous emulsion to the polymerization reaction which contains at least 80% of the surfactant used in the emulsion polymerization.
  • a seed latex is a polymer latex which is present in the aqueous polymerization medium before the polymerization of 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 a 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 is 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 selected from the group consisting of C 2 -C 10 -alkyl esters of acrylic acid, in particular ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethyl-hexylacrylate, C r C 4 - alkyl methacrylates such as methyl methacrylate, monoethylenically unsaturated nitriles, such as acrylonitrile and vinylaromatic monomers as defined above such as styrene and mixtures thereof.
  • monomers selected from the group consisting of C 2 -C 10 -alkyl esters of acrylic acid, in particular ethyl acrylate, n-butyl acrylate
  • the polymer particles of the seed latex is 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 selected from the group consisting of C 1 -C 4 -alkyl methacrylates such as methyl methacrylate, monoethylenically unsaturated nitriles, such as acrylonitrile and vinylaromatic monomers as defined above such as styrene and mixtures thereof.
  • C 1 -C 4 -alkyl methacrylates such as methyl methacrylate
  • monoethylenically unsaturated nitriles such as acrylonitrile
  • vinylaromatic monomers as defined above such as styrene and mixtures thereof.
  • the seed latex is usually charged into the polymerization vessel before the polymerization of the monomers M is started.
  • the seed latex is charged into the polymerization 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 free-radical initiator into the polymerization vessel before the addition of the monomers M is started. However, it is also possible to add the monomers M 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 of 0.01 to 10% by weight, preferably in the range of 0.05 to 5% by weight, in particular in the range of 0.05 to 3% by weight, based on the total weight of the monomers in the monomer composition M to be polymerized.
  • the free-radical aqueous emulsion polymerization of the invention can be carried out at temperatures in the range from 0 to 170°C. Temperatures employed are generally in the range from 50 to 120°C, frequently 60 to 120°C and often 70 to 110°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.
  • emulsion polymerizations are conducted under reduced pressure, pressures of 950 mbar, frequently of 900 mbar and often 850 mbar (absolute) are established.
  • 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 process for producing the polymer latex of the present invention may be a single stage polymerization or a multistage emulsion polymerization.
  • a single stage polymerization the overall composition of the monomers M, which are fed to the polymerization reaction under polymerization conditions, remains the same or almost the same, while in a multistage emulsion polymerization the overall composition of the monomers M, which are fed to the polymerization reaction under polymerization conditions, is altered at least once, in particular such that the theoretical glass transition temperature of the resulting polymer formed in one stage differs from the theoretical glass transition temperature of the resulting polymer formed in another stage by at least 10°C, in particular by at least 20°C or at least 40°C.
  • the process of the invention is performed as a 2-stage emulsion polymerization, i.e. the composition of the monomers, which are fed to the polymerization reaction under polymerization conditions, is amended once, or as a 3- or 4-stage emulsion polymerization, i.e. the composition of the monomers, which are fed to the polymerization reaction under polymerization conditions, is amended twice or trice.
  • Chain transfer agents are understood to mean compounds that transfer free radicals, and which reduce the molecular weight of the growing chain and/or which 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-but
  • 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 2% by weight, in particular 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 2% by weight and may be as high as 8% by weight, in particular at most 4% by weight, based on the total amount of monomers M added to the polymerization reaction during said period.
  • aqueous polymer dispersion obtained on completion of polymerization of the monomers M is subjected to an after-treatment to reduce the residual monomer content.
  • This after-treatment is effected either chemically, for example by completing the polymerization reaction using a more effective free- radical initiator system (known as postpolymerization), and/or physically, for example by stripping the aqueous polymer dispersion with steam or inert gas.
  • the aqueous polymer dispersion obtained by the process of the invention is frequently neutralized prior to formulating it as a coating composition.
  • the neutralization of acid groups of the polymer is achieved by neutralizing agents known to the skilled of the art after polymerization and/or during the polymerization.
  • the neutralizing agent may be added in a joint feed with the monomers to be polymerized or in a separate feed.
  • Suitable neutralizing agents include organic amines, alkali hydroxides, ammonium hydroxides. In particular, neutralization is achieved by using ammonia or alkali hydroxides such as sodium hydroxide or potassium hydroxide.
  • post-curing agent also termed as post-crosslinking agent
  • post-crosslinking agent will result in a crosslinking reaction during and/or after film formation by forming coordinative or covalent bonds with reactive sites on the surface of the polymer particles.
  • Crosslinking agents which are suitable for providing post crosslinking, are for example compounds having at least two functional groups selected from oxazoline, amino, aldehyde, aminoxy, carbodiimide, aziridinyl, epoxy and hydrazide groups, derivatives or compounds bearing acetoacetyl groups. These crosslinkers react with reactive sites of the polymers of the polymer dispersion which bear complementary functional groups in the polymer, which are capable of forming a covalent bond with the crosslinker. Suitable systems are known to skilled persons.
  • post-crosslinking can be achieved by formulation of the polymer dispersion with one or more polycarbodiimides as described in US 4977219, US 5047588, US 5117059, EP 0277361, EP 0507407, EP 0628582, US 5352400, US 2011/0151128 and US 2011/0217471. It is assumed that crosslinking is based on the reaction of the carboxyl groups of the polymers with polycarbodiimides. The reaction typically results in covalent cross-links which are predominately based on N-acyl urea bounds (J.W. Taylor and D.R. Bassett, in E.J. Glass (Ed.), Technology for Waterborne Coatings, ACS Symposium Series 663, Am. Chem. Soc., Washington, DC, 1997, chapter 8, pages 137 to 163).
  • a suitable post-curing agent may also be a water-soluble or water-dispersible polymer bearing oxazoline groups, e.g. the polymers as described in US 5300602 and WO 2015/197662.
  • Post crosslinking can also be achieved by analogy to EP 1227116, which describes aqueous two-component coating compositions containing a binder polymer with carboxylic acid and hydroxyl functional groups and a polyfunctional crosslinker having functional groups selected from isocyanate, carbodiimide, aziridinyl and epoxy groups.
  • post-crosslinking can be achieved by formulating the aqueous polymer dispersion with one or more dihydrazides, in particular aliphatic dicarboxylic acid such as adipic acid dihydrazide (ADDH) as described in US 4931494, US 2006/247367 and US 2004/143058.
  • dihydrazides in particular aliphatic dicarboxylic acid such as adipic acid dihydrazide (ADDH) as described in US 4931494, US 2006/247367 and US 2004/143058.
  • Suitable agents of achieving post-curing include epoxysilanes to crosslink carboxy groups in the polymer; dialdehydes such as glyoxal to crosslink urea groups or acetoacetoxy groups, such as those derived from the monomers M5b and M5c, respectively, as defined herein, in particular ureido (meth)acrylate or acetoacetoxyethyl (meth)acrylate; di- and/or polyamines to crosslink keto groups or epoxy groups such as those derived from the monomers M5c or M6b as defined herein; and
  • acetophenones such as 2-hydroxy-2,2-dimethylacetophenone, 2-phenyl-2,2- dimethylacetophenone
  • cycloalkylphenyl ketones such as 1-benzoyl
  • Suitable systems are e.g. described in EP 355028, EP 441221, EP 0789724, US 5516453 and US 5498659 and/or commercially available, e.g. in case of UV initiators from Omnirad and IGM Resins (e.g. Esacure TZM, Esacure TZT, Omnirad 4MBZ).
  • the present invention also relates to waterborne coating compositions, which contain a) a binder polymer in the form of the aqueous polymer latex as defined herein; and b) at least one further ingredient, which is conventionally used in waterborne coating compositions and which is not a binder.
  • the waterborne coating compositions of the invention may be formulated as a clear coat or a as a paint.
  • the waterborne coating compositions at least one inorganic pigment, which imparts a white shade or a color to the coating obtained when using the waterborne coating composition for coating substrates.
  • 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 55944:2003-11.
  • pigments are in particular inorganic pigments, such as white pigments like titanium dioxide (C.l. Pigment White 6), but also color pigments, e.g. black pigments, such as iron oxide black (C.l. Pigment Black 11), iron manganese black, spinel black (C.l. Pigment Black 27), carbon black (C.l. Pigment Black 7); color pigments, such as chromium oxide, chromium oxide hydrate green; chrome green (C.l. Pigment Green 48); cobalt green (C.l.
  • Pigment Green 50 ultramarine green; cobalt blue (C.l. Pigment Blue 28 und 36); ultramarine blue, iron blue (C.l. Pigment Blue 27), manganese blue, ultramarine violet, cobalt violet, manganese violet, iron oxide read (C.l. Pigment Red 101); cadmium sulfoselenide (C.l. Pigment Red 108); molybdate read (C.l. Pigment Red 104); ultramarine read, iron oxide brown, mixed brown, spinel- and Korundum phases (C.l. Pigment Brown 24, 29 und 31), chrome orange; iron oxide yellow (C.l. Pigment Yellow 42); nickel titanium yellow (C.l. Pigment Yellow 53; C.l.
  • Pigment Yellow 157 und 164 chrome titanium yellow; cadmium sulfide und cadmium zinc sulfide (C.l. Pigment Yellow 37 und 35); Chrome yellow (C.l. Pigment Yellow 34), zinc yellow, alkaline earth metal chromates; Naples yellow; bismuth vanadate (C.l. 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.
  • the water-borne coating compositions may also contain one or more fillers.
  • 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.
  • 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 Syloid® brands from W. R. Grace & Company and the Acematt® brands from Evonik GmbH. Organic flatting agents are obtainable, for example, from BYK-Chemie GmbH under the Ceraflour® brands and the Ceramat® brands, and from Deuteron GmbH under the Deuteron MK® brand.
  • the proportion of the pigments and fillers in the water-borne coating compositions can be described in a manner known per se via the pigment volume concentration (PVC).
  • the water-borne coating compositions are formulated as a paint, they usually have a pigment volume concentration (PVC) of at least 5%, especially at least 10% and will typically not exceed 90%, in particular 85%.
  • PVC pigment volume concentration
  • the PVC will not exceed a value of 60%, especially 50%, and is specifically in the range from 5 to 60% or 5 to 50%.
  • the inventive effects of the polymer dispersions are also manifested in varnishes which typically have a pig ment/fil ler content below 5% by weight, based on the varnish, and correspondingly have a PVC below 5%.
  • the PVC will be in the range of >60 to 90%, in particular in the range of 65 to 85%.
  • the water-borne coating compositions of the invention are designed as a paint containing white pigment - that is, they comprise at least one white pigment and optionally one or more fillers.
  • white pigment they include, in particular, titanium dioxide, preferably in the rutile form, optionally in combination with one or more fillers.
  • the coating compositions of the invention comprise a white pigment, more particularly titanium dioxide, preferably in the rutile form, in combination with one or more fillers, such as chalk, talc or mixtures thereof, for example.
  • the water-borne coating compositions of the invention are designed as a clear-coat or as a wood-stain formulation.
  • clear-coats are essentially devoid of pigments and fillers, while wood stains do not contain much fillers, i.e. they have a PVC of below 5%.
  • the present invention also relates to a waterborne coating composition (hereinafter also referred to as aqueous coating composition) comprising: i) at least one aqueous polymer latex as defined above; and ii) a titanium dioxide pigment.
  • a waterborne coating composition hereinafter also referred to as aqueous coating composition
  • aqueous coating composition comprising: i) at least one aqueous polymer latex as defined above; and ii) a titanium dioxide pigment.
  • the present invention also relates to the use of the aqueous polymer latex as a binder in an aqueous coating composition containing a titanium dioxide pigment.
  • the aqueous polymer latex is combined with a TiO 2 pigment slurry or paste.
  • the TiO 2 concentration of an aqueous TiO 2 pigment slurry or paste used for preparing the aqueous coating composition will generally be in the range from 30% to 85% by weight, frequently 40% to 80% by weight and, based in each case on the total weight of the aqueous TiO 2 pigment slurry or paste.
  • the titanium dioxide pigment used for preparing the aqueous dispersion of the pigment slurry or paste may be any TiO 2 pigment conventionally used in coating compositions, in particular in aqueous coating compositions. Frequently, a TiO 2 pigment is used wherein the TiO 2 particles are preferably in the rutile form. In another preferred embodiment the TiO 2 particles can also be coated e.g. with aluminum, silicon and zirconium compounds.
  • the weight ratio of the polymer to the titanium dioxide pigment is in the range of > 0.1:5.0 to ⁇ 5.0:0.1; preferably the weight ratio of the polymer to the titanium dioxide pigment is in the range of > 0.5:5.0 to ⁇ 5.0:0.5; in particular more preferably the weight ratio of the polymer to the titanium dioxide pigment is in the range of > 0, 5:3.0 to ⁇ 3.0:0, 5 and in particular in the range of > 0.5:1.5 to ⁇ 1.5:0.5.
  • the titanium dioxide pigment has an average primary particle size in the range of > 0.1 pm to ⁇ 0.5 pm, as determined by light scattering or by electron microscopy.
  • the aqueous coating composition further comprises at least one additive selected from the group consisting of thickeners, defoamers, levelling agents, filming auxiliaries, biocides, wetting agents or dispersants, fillers and coalescing agents.
  • the aqueous coating composition can be simply prepared by mixing TiO 2 pigment powder or an aqueous slurry or paste of TiO 2 pigment with the aqueous polymer latex of the invention, preferably by applying shear to the mixture, e.g. by using a dissolver conventionally used for preparing water-borne paints. It will also be possible to prepare an aqueous slurry or paste of TiO 2 pigment and the aqueous polymer latex of the invention, which is then incorporated into or mixed with further polymer latex of the invention or with any other polymer latex binder.
  • the aqueous dispersion of the polymer composite may also be prepared by incorporating the aqueous polymer latex of the invention as a binder or co-binder in an aqueous base formulation of a paint, which already contains a TiO 2 pigment, e.g. by mixing the aqueous polymer latex of the invention with a pigment formulation that already contains further additives conventionally used in the paint formulation.
  • the mixing may optionally be performed in the presence of additives conventionally used in aqueous pigment slurries or pigment pastes, such as dispersants.
  • Suitable dispersants include but are not limited to, for example, polyphosphates such as sodium polyphosphates, potassium polyphosphates or ammonium polyphosphates, alkali metal salts and ammonium salts of acrylic acid homo- or copolymers or maleic anhydride polymers, polyphosphonates, such as sodium 1 -hydroxyethane-1 ,1 -diphosphonate, and naphthalenesulfonic salts, especially the sodium salts thereof.
  • the polymer concentration in the aqueous polymer latex used for preparing the aqueous dispersion of the polymer composite is generally in the range from 10% to 70% by weight, preferably 20% to 65% by weight and most preferably 30% to 60% by weight, based in each case on the total weight of the aqueous polymer latex.
  • the aqueous coating compositions may contain one or more pigments different from the TiO 2 pigment and/or fillers as described above.
  • the waterborne coating compositions comprise at least one aqueous polymer latex as defined herein, further comprises a rheology modifying agent.
  • Suitable rheology modifying agents include associative thickener polymers and non-associative rheology modifiers.
  • the aqueous liquid composition preferably comprises a thickening agent selected from the group consisting of associative thickeners and a non-associative thickener and combinations thereof.
  • Associative thickener polymers are well known and frequently described in the scientific literature, e.g. by E.J. Schaller et al., "Associative Thickeners” in Handbook of Coating Additives, Vol. 2 (Editor L.J. Calbo), Marcel Decker 192, pp. 105-164, J. Bieleman “PUR- Verdicker” in Additives for Coatings (Editor J. Bielemann), Wiley 2000, pp 50 - 58.
  • NiSAT thickener polymers of the HEUR and HMPE type are also described in the patent literature, such as US 4,079,028, US 4155,892, EP 61822, EP 307775, WO 96/31550, EP 612329, EP 1013264, EP 1541643, EP 1584331, EP 2184304, DE 4137247, DE 102004008015, DE 102004031786, US 2011/0166291 and WO 2012/052508.
  • associative thickener polymers are commercially available.
  • the associative thickener polymers include anionic, acrylate type thickener polymers, so-called HASE polymers (hydrophobically modified polyacrylate thickeners), which are copolymers of acrylic acid and alkyl acrylate monomers, where the alkyl group of the alkyl acrylate may have from 6 to 24 carbon atoms.
  • HASE polymers hydrophobically modified polyacrylate thickeners
  • the associative thickener polymers also include non-ionic associative thickeners, so called NiSAT thickeners (non-ionic synthetic associative thickeners), which usually are linear or branched block copolymers having at least one interior hydrophilic moiety, in particular a polyether moiety, especially at least one polyethylene oxide moiety and two or more terminal hydrocarbon groups each having at least 4 carbon atoms, in particular from 4 to 24 carbon atoms, e.g. a linear or branched alkyl radical having 4 to 24 carbon atoms or alkyl substituted phenyl having 7 to 24 carbon atoms.
  • NiSAT thickeners include the hydrophobically modified polyethylene oxide urethane rheology modifiers, also termed HEUR or PUR thickeners, and hydrophobically modified polyethyleneoxides, which are also termed HMPE.
  • the amount of the associative 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 0.2 to 2% by weight, based on the latex paint.
  • Suitable non-associative rheology modifiers are in particular cellulose-based thickeners, especially hydroxyethyl cellulose, but also thickeners based on acrylate emulsions (ASE). Amongst the non-associative rheology modifiers preference is given to non-associative cellulose based thickeners.
  • the total amount of the thickener polymer will depend on the desired viscosity profile and is frequently in the range from 0.05 to 6% by weight, in particular 0.1 to 5.5% by weight of thickener, and especially 0.15 to 5% by weight, based on the latex paint.
  • the aqueous coating compositions of the invention may also comprise customary auxiliaries.
  • the customary auxiliaries will depend from the kind of the coating in a well- known manner and include but are not limited to: wetting agents or dispersants, filming auxiliaries, also termed coalescents, leveling agents, UV stabilizers, biocides and defoamers/de-aerators.
  • 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 low 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 (Texanol®) and the glycol ethers and esters, commercially available, for example, from BASF SE under the Solvenon® and Lusolvan® and Loxanol® names, and from Dow under the Dowanol® trade name.
  • the amount is preferably ⁇ 5% by weight and more preferably ⁇ 1% by weight, based on the overall formulation. Formulation is also possible completely without filming auxiliaries. Frequently, the coating compositions do not require any filming auxiliaries.
  • auxiliaries and components are e.g. described by J. Bieleman in “Additives for Coatings", Whiley-VCH, Weinheim 2000; by T. C. Patton in “Paint Flow and Pigment Dispersions", 2nd Edition, John Whiley & Sons 1978; and by M. Schwartz and R. Baumstark in “Water based Acrylates for Decorative Coatings", Curt R. Vincentz Verlag, Hanover 2001.
  • the waterborne coating compositions of the invention may also be formulated as a low VOC paint.
  • concentration of volatile compounds in the coating composition is preferably below 0.1 wt.-%, more preferably below 0.05 wt.-%, based on the total amount of the waterborne coating composition.
  • a volatile compound in terms of the invention is a compound, which has a boiling point at 1013 mbar of less than 250°C.
  • the waterborne coating compositions of the invention are particularly useful in architectural coatings, i.e. for coating exterior or interior parts of a building.
  • the substrate may be a mineral substrate, such as plaster, gypsum, plasterboard or concrete, wood, wood-based materials, metal, wallpaper or plastic, such as PVC.
  • the waterborne coating compositions can be applied to substrates to be coated in a customary manner, for example by applying it with brushes or rollers, by spraying, by dipping, by rolling, or by bar coating to the desired substrate. Preferred applications are by brush and/or by roller.
  • the coating of substrates is effected in such a way that the substrate is first coated a waterborne coating composition of the invention, and then the thus obtained aqueous coating is subjected to a drying step, especially within the temperature range of > -10 and ⁇ +50°C, advantageously > +5 and ⁇ +40°C and especially advantageously > +10 and ⁇ +35°C.
  • the substrates coated with a waterborne coating composition of the invention have excellent resistance to whitening on exposure to water or to weathering conditions. Moreover, the coatings have good adhesion properties such as high dry alkyd adhesion, good opacity, high block resistance, good stain removal properties, high wet scrub resistance and low dirt pick-up.
  • the present invention also relates to waterborne adhesive compositions, which contain a) a binder polymer in the form of the aqueous polymer latex as defined herein; and b) at least one additional ingredient, which is conventionally used in waterborne adhesive compositions and which is not a binder.
  • the waterborne adhesive compositions of the invention typically contain, besides the polymer latex, more than one additional ingredient well known in the art, such as additives including but not limited to, for example, rheology modifiers, plasticizers, tackifiers, defoamers, wetting agents, biocides and adhesion promoters, where the rheology modifiers, plasticizers, defoamers, wetting agents and biocides may be selected from those mentioned herein above.
  • the waterborne adhesive compositions of the invention may contain further or other additional ingredients that are also well established in the art.
  • Formulations of aqueous adhesive compositions of the invention suitable for particular adhesive applications comprise certain amounts of a specific binder polymer and of at least one, usually two or more, specific additional ingredients. The exact nature of all these components and their amounts useful in preparing such formulations can usually be determined in a manner known per se. les
  • room temperature and “ambient temperature” means a temperature in the range of 22-23°C.
  • 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 130°C in a drying cabinet (2 hours). Two separate measurements were conducted. The values reported in the examples each are the mean of the two measurements.
  • average particle diameter of the polymer latex was determined by dynamic light scattering (DLS) as described above, using a Malvern HPPS.
  • 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).
  • pH measurements were performed on reaction mixtures, using a pH meter.
  • Isobutyl acrylate can be prepared by analogy to the protocol for producing bio-isoamyl acrylate described in WO 2022/018013 by transesterification of ethyl acrylate with isobutanol.
  • a pressure of 860 mbar and a bath temperature of 125°C were then set. 24.1 g titanium tetraisopropoxylate were added as catalyst. After the start of boiling, an azeotrope of ethyl acrylate and ethanol was continuously distilled off with a reflux ratio of initially 10:7, which was varied during the course of the reaction. The sump temperature increased to a maximum of 102 °C during the course of the reaction, and the vacuum was adjusted up to 610 mbar. Distillate and sump samples were taken at regular intervals to monitor the progress of the reaction. To accelerate the conversion, further catalyst was added in portions (34.6 g in total) during the course of the reaction. After 6.6 h of distillation time, the conversion was >97.5%.
  • ethyl acrylate was distilled off at a bath temperature of 115°C, and the vacuum was gradually reduced to 335 mbar.
  • 300 ml of water were added, stirred for 1 h at a bath temperature of 100°C, and then the water was distilled off. During the distillation, the pressure was reduced to 12 mbar.
  • 60 g of Harbolite 900 filter aid were added and filtered through a pressure filter funnel.
  • a pressure of 860 mbar and a bath temperature of 125°C were then set. 22.4 g titanium tetraisopropoxylate were added as catalyst. After the start of boiling, an azeotrope of ethyl acrylate and ethanol was continuously distilled off with a reflux ratio of initially 10:3, which was varied during the course of the reaction. The sump temperature increased to a maximum of 102 °C during the course of the reaction, and the vacuum was adjusted up to 610 mbar. Distillate and sump samples were taken at regular intervals to monitor the progress of the reaction. To accelerate the conversion, further catalyst was added in portions (45.1 g in total) during the course of the reaction. After 8.8 h of distillation time, the conversion was 97.4%.
  • the reaction mixture was heated with stirring and lean air sparging. At a sump temperature of 90-120 °C, an azeotrope of cyclohexane and water was distilled off. During this process the aqueous phase formed in the water separator was discarded and the organic phase was transferred back to the reactor. After 99 g of water had been distilled off within 8.3 h, the reaction mixture was cooled down to room temperature. The organic phase was extracted first with 450 g of water, then with 260 g of an aqueous 12.5% NaOH solution and finally with 450 g of water.
  • a reactor equipped with stirrer, temperature control, nitrogen inlet and several injection possibilities was charged with 244.3 g deionized water, 27.3 g polystyrene seed dispersion (33 wt%, particle diameter: 30 nm).
  • the reaction mixture was purged with nitrogen and heated to 85°C. At 85°C 5.0 g of feed 2 were added. After 5 min, feed 1 and feed 2 were added in 180 min.
  • Feed 1 400.5 g deionized water, 18.5 g Dowfax 2A1, 20.8 g Lutensol TO 82, 6.9 g acrylic acid, 13.9 g acrylamide (50 wt% aqueous solution), 282.6 g 1-heptyl acrylate, 401.2 g methyl methacrylate.
  • Feed 2 19.8 g aqueous sodium persulfate solution (7 wt%).
  • the reaction mixture was post-polymerized at 85°C for 30 min. Then feed 3 and feed 4 were added in 60 min.
  • Feed 3 6.9 g aqueous t-butylhydroperoxide solution (10 wt%).
  • Feed 4 6.2 g aqueous Rongalit C solution (10 wt%).
  • reaction mixture was cooled down to ambient temperature and neutralized with sodium hydroxide to pH 8-9.
  • Average particle diameter 140 nm
  • a reactor equipped with stirrer, temperature control, nitrogen inlet and several injection possibilities was charged with 244.3 g deionized water, 27.3 g polystyrene seed dispersion (33 wt%, particle diameter: 30 nm).
  • the reaction mixture was purged with nitrogen and heated to 85°C. At 85°C 5.0 g of feed 2 were added. After 5 min, feed 1 and feed 2 were added in 180 min.
  • Feed 1 400.5 g deionized water, 18.5 g Dowfax 2A1, 20.8 g Lutensol TO 82, 6.9 g acrylic acid, 13.9 g acrylamide (50 wt% aqueous solution), 104.7 g 1-heptyl acrylate, 272.1 g isobutyl acrylate, 307.0 g methyl methacrylate.
  • Feed 2 19.8 g aqueous sodium persulfate solution (7 wt%).
  • the reaction mixture was post-polymerized at 85°C for 30 min. Then feed 3 and feed 4 were added in 60 min.
  • Feed 3 6.9 g aqueous t-butylhydroperoxide solution (10 wt%).
  • Feed 4 6.2 g aqueous Rongalit C solution (10 wt%).
  • reaction mixture was cooled down to ambient temperature and neutralized with sodium hydroxide to pH 8-9.
  • a reactor equipped with stirrer, temperature control, nitrogen inlet and several injection possibilities was charged with 244.3 g deionized water, 27.3 g polystyrene seed dispersion (33 wt%, particle diameter: 30 nm).
  • the reaction mixture was purged with nitrogen and heated to 85°C. At 85°C 5.0 g of feed 2 were added. After 5 min, feed 1 and feed 2 were added in 180 min.
  • Feed 1 400.5 g deionized water, 18.5 g Dowfax 2A1, 20.8 g Lutensol TO 82, 6.9 g acrylic acid, 13.9 g acrylamide (50 wt% aqueous solution), 104.7 g 1-heptyl acrylate, 209.3 g n-butyl acrylate, 369.8 g methyl methacrylate.
  • Feed 2 19.8 g aqueous sodium persulfate solution (7 wt%).
  • the reaction mixture was post-polymerized at 85°C for 30 min. Then feed 3 and feed 4 were added in 60 min.
  • Feed 3 6.9 g aqueous t-butylhydroperoxide solution (10 wt%).
  • Feed 4 6.2 g aqueous Rongalit C solution (10 wt%).
  • reaction mixture was cooled down to ambient temperature and neutralized with sodium hydroxide to pH 8-9.
  • a reactor equipped with stirrer, temperature control, nitrogen inlet and several injection possibilities was charged with 244.3 g deionized water, 27.3 g polystyrene seed dispersion (33 wt%, particle diameter: 30 nm).
  • the reaction mixture was purged with nitrogen and heated to 85°C. At 85°C 5.0 g of feed 2 were added. After 5 min, feed 1 and feed 2 were added in 180 min.
  • Feed 1 400.5 g deionized water, 18.5 g Dowfax 2A1, 20.8 g Lutensol TO 82, 6.9 g acrylic acid, 13.9 g acrylamide (50 wt% aqueous solution), 346.4 g methyl methacrylate, 332.6 g n-butyl acrylate.
  • Feed 2 19.8 g aqueous sodium persulfate solution (7 wt%).
  • the reaction mixture was post-polymerized at 85°C for 30 min. Then feed 3 and feed 4 were added in 60 min.
  • Feed 3 6.9 g aqueous t-butylhydroperoxide solution (10 wt%).
  • Feed 4 6.2 g aqueous Rongalit C solution (10 wt%).
  • reaction mixture was cooled down to ambient temperature and neutralized with sodium hydroxide to pH 8-9.
  • the mixture was filtered through a 400 pm filter and then added to a combination of 490.7 g binder from Example E1, 25.0 g Ropaque Ultra E polymeric pigment (Dow) and 2.0 g Foamstar 2420 defoamer (BASF) and stirred for 5 min.
  • 9.0 g Texanol coalescing agent (Eastman) and 5.0 g Optifilm 400 coalescing agent (Eastman) were added and mixed for 5 min.
  • 2.0 g Proxel AQ biocide (Lonza), 3.0 g Polyphase 663 fungicide (Troy Corporation) and 2.9 g Rheolate CVS 10 non-ionic associative thickener (Elementis) were added and mixed for 5 min.
  • 1.0 g Acrysol RM 895 non-ionic associative thickener (Dow) was added and the mixture was stirred for 30 min at medium speed.
  • Formulation of semi-gloss paint with binder from Example E2 200.0 g Kronos 4311 pigment was mixed with 15.0 g water. At low stirring speed 1.75 g AMP-95 neutralizer (Angus Chemical Company), 5.0 g propylene glycol (Univar), 2.0 g Foamstar 2420 defoamer (BASF), 10.0 g Tamol 165 A dispersant (Dow) and 3.0 g Hydropalat WE 3320 wetting agent (BASF) were added.
  • At high stirring speed 1.5 g Attagel 50 (BASF), 25.0 g Minex 10 (Sibelco) filler, 125.0 g Kronos 4311 pigment, 98.1 g water and 20.0 g Aquaflow NHS-310 (Ashland) non-ionic associative thickener were added and mixed for 30 min. The mixture was filtered through a 400 pm filter and then added to a combination of 501.9 g binder from Example E2, 25.0 g Ropaque Ultra E polymeric pigment (Dow) and 2.0 g Foamstar 2420 defoamer (BASF) and stirred for 5 min.
  • BASF Attagel 50
  • 25.0 g Minex 10 (Sibelco) filler 125.0 g Kronos 4311 pigment, 98.1 g water and 20.0 g Aquaflow NHS-310 (Ashland) non-ionic associative thickener were added and mixed for 30 min. The mixture was filtered through a 400 pm filter and then added to a combination of 501.9 g binder from Example
  • the mixture was filtered through a 400 pm filter and then added to a combination of 494.7 g binder from Example E3, 25.0 g Ropaque Ultra E polymeric pigment (Dow) and 2.0 g Foamstar 2420 defoamer (BASF) and stirred for 5 min.
  • 9.0 g Texanol coalescing agent (Eastman) and 5.0 g Optifilm 400 coalescing agent (Eastman) were added and mixed for 5 min.
  • 2.0 g Proxel AQ biocide (Lonza), 3.0 g Polyphase 663 fungicide (Troy Corporation) and 2.0 g Rheolate CVS 10 non-ionic associative thickener (Elementis) were added and mixed for 5 min.
  • 1.0 g Acrysol RM 895 non-ionic associative thickener (Dow) was added and the mixture was stirred for 30 min at medium speed.
  • the mixture was filtered through a 400 pm filter and then added to a combination of 495.7 g binder from Example C1, 25.0 g Ropaque Ultra E polymeric pigment (Dow) and 2.0 g Foamstar 2420 defoamer (BASF) and stirred for 5 min.
  • 9.0 g Texanol coalescing agent (Eastman) and 5.0 g Optifilm 400 coalescing agent (Eastman) were added and mixed for 5 min.
  • 2.0 g Proxel AQ biocide (Lonza), 3.0 g Polyphase 663 fungicide (Troy Corporation) and 2.5 g Rheolate CVS 10 non-ionic associative thickener (Elementis) were added and mixed for 5 min.
  • 1.0 g Acrysol RM 895 non-ionic associative thickener (Dow) were added and the mixture was stirred for 30 min at medium speed.
  • a coating film was prepared with a 3 mils drawdown bar on a Leneta 3B black and white sealed drawdown card. The film was dried at room temperature for 24 hours. Gloss was measured with a gloss meter at angles of 20°, 60° and 80°, respectively. The results were as follows:
  • High shear viscosity was measured according to ASTM D4287, 7 days after preparation.
  • a coating film was prepared with a 3 mils drawdown bar on a Leneta 3B black and white sealed drawdown card. The film was dried at room temperature for 24 hours. The opacity was determined spectrophotometrically as the ratio of reflected light from the dried coating over the black portions and the white portions of the Leneta card. The opacity indicates the capability of the coating to hide the black surface. The results were as follows:
  • Dry alkyd adhesion is improved for E4 compared to C2.
  • Kbnig pendulum hardness was measured according to ASTM D4366, using aluminum as the coating substrate. Evaluation was conducted after 7 days. The following results each reflect the average number of oscillations of three measurements.
  • Stain removal was measured according to ASTM D4828.
  • the results for the coatings from E4, E5 and E6 were comparable to those from C2 for pencil, lipstick, crayon, ballpen, red wine, ketchup, coffee and mustard (visual inspection).
  • the mill glaze on yellow pine wood surface was scrubbed with water and dried overnight.
  • the substrate was divided into sections depending on the number of samples to be tested. Using the appropriate brush, the test paint samples were applied at natural spread rate. The coatings were cured at room temperature for the period of 4 hours and 24 hours, respectively. Then, half of the coated area was covered with 2 inches of dry dirt (Arizona or Carpet soil). The panel was allowed to sit for 15 minutes, then tilted vertically and tapped to release dirt. The dirty area of each sample was lightly brushed (15 strokes).
  • Scrub resistance was measured according to ASTM D2486. The number of scrub cycles until failure occurred was determined.

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Abstract

La présente invention concerne donc des latex polymères aqueux de copolymères pouvant être obtenus par polymérisation en émulsion aqueuse de monomères à insaturation éthylénique M, qui comprennent i. 5 à 90 % en poids, en particulier 10 à 70 % en poids, en particulier 10 à 50 % en poids, sur la base de la quantité totale de monomères M, d'un monomère M1, qui est l'acrylate de 1-heptyle ; ii. 0 à 70 % en poids, par rapport à la quantité totale de monomères M, d'au moins un monomère M2 choisi parmi les esters d'alkyle d'acide acrylique en C2-C6 à l'exception de l'acrylate de tert-butyle, les esters d'alkyle en C8-C20 d'acide acrylique et les esters d'alkyle en C5-C20 d'acide méthacrylique et leurs mélanges ; iii. 5 à 70 % en poids, par rapport à la quantité totale de monomères M, d'au moins un monomère M3 choisi parmi l'acrylate de tert-butyle, les esters d'alkyle en C1-C4 d'acide méthacrylique, les esters de cycloalkyle d'acide acrylique en C5-C20, les esters de cycloalkyle d'acide méthacrylique en C5-C20, de cycloalkylméthyle d'acide acrylique en C5-C20, de cycloalkylméthyle esters d'acide méthacrylique en C5-C20, le cycloalkyle dans les monomères précités étant mono, bi ou tricyclique et où 1 ou 2 fractions CH2 non adjacentes de cycloalkyle peuvent être remplacées par des atomes d'oxygène et où le cycloalkyle peut être non substitué ou porter 1, 2, 3 ou 4 groupes méthyle, et les monomères aromatiques monovinyliques, le méthylène-gamma-butyrolactone et leurs mélanges ; la quantité totale de monomères M1 et M2 étant dans la plage de 10 à 90 % en poids, sur la base de la quantité totale de monomères à insaturation éthylénique M, et la quantité totale de monomères M1, M2 et M3 étant d'au moins 90 % en poids, sur la base de la quantité totale de monomères à insaturation éthylénique M. La présente invention concerne également un processus de production des latex polymères aqueux de la présente invention. La présente invention concerne également l'utilisation de ces latex polymères en tant que liants dans des compositions de revêtement à l'eau et des compositions adhésives à l'eau, en particulier en tant que liants dans des compositions de revêtement à base d'eau.
PCT/EP2024/072966 2023-08-16 2024-08-15 Latex polymère aqueux de copolymères approprié comme liant dans des compositions de revêtement à base d'eau WO2025036959A1 (fr)

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