Aqueous polymer latex of film-forming copolymers suitable as binder in waterborne coating compositions

Abstract

by weight, based on the total amount of ethylenically unsaturated monomers M. The present invention also relates to a process for producing the aqueous polymer latexes of the present invention by emulsion polymerization. The present invention also relates to the use of these polymer latexes as binders or co-binders in waterborne coating compositions, in particular in waterborne compositions for wood coating, such as waterborne wood stain formulations, waterborne wood paint formulations and waterborne clearcoat formulations for wooden surfaces, but also for waterborne architectural coatings and for interior coatings.

Description

[Technical Field]

[0001] This invention relates to aqueous polymeric latexes of film-forming copolymers obtainable by aqueous emulsion polymerization of olefinic unsaturated monomers M, wherein the monomers M are based on monomers M comprising at least 90% by weight of at least two different nonionic monomers selected from acrylate monomers, methacrylate monomers, and monovinyl aromatic monomers. This invention also relates to processes for producing such polymeric latexes and to the use of such polymeric latexes as binders in water-based coating compositions, specifically latex paints, particularly latex paints for architectural coatings and wood coatings (e.g., wood paints and wood stains). [Previous Technology]

[0002] As is well known, polymeric latexes (also known as polymeric dispersions) can be specifically used as binders or binder components in coating compositions, also referred to as co-binders. For binders or co-binders in coating compositions, an important requirement is that they provide the coating with hardness and anti-blocking properties. In addition, polymeric latexes should provide the coating with low water absorption, good weather resistance (specifically against moisture and UV radiation exposure), and good flexibility.

[0003] US 4,267,091 describes an adhesive composition for use in paints and dry-bonded lime plaster, comprising A) a polymer latex obtained by emulsion polymerization of olefinic unsaturated monomers, including alkyl (meth)acrylates (as the main monomer component) and carbonyl monomers (e.g., methyl styrene and diacetone acrylamide), B) a dihydrazine compound, and C) a water-soluble zinc salt.

[0004] WO 2011 / 009874 describes an aqueous polymer dispersion based on olefinic unsaturated monomers, wherein the olefinic unsaturated monomers include 20% to 75% by weight of tributyl methacrylate. The polymer latex provides improved flame retardancy and is therefore particularly suitable for the production of architectural coatings, thermal insulation coatings and structural adhesives.

[0005] WO 2012 / 130712 describes a polymer latex obtained by two-stage emulsion polymerization and its use as a binder in water-based coating compositions for wood coatings. The polymer dispersion exhibits good storage stability and the coating compositions obtained from it produce coatings with good wet adhesion and good hardness.

[0006] WO 2014 / 07595 describes the use of polymer latex as a binder for improving the color retention of exterior coatings, wherein the polymer latex comprises at least two different monomers whose homopolymers have a theoretical glass transition temperature of at least 25°C and at least two different monomers whose homopolymers have a theoretical glass transition temperature of less than 25°C.

[0007] WO 2016 / 042116 describes a polymer dispersion prepared by two-stage emulsion polymerization in the presence of a copolymerizable emulsifier and its use as a binder in water-based coating compositions for wood coatings. The coating compositions prepared therefrom produce coatings with good water resistance and good hardness.

[0008] Despite progress in many areas, providing polymer dispersions with balanced application characteristics remains a challenging task, as both application properties and the stability of the polymer dispersion must be considered. Specifically, it is difficult to simultaneously coordinate the different coating property requirements using a binder. Often, attempting to improve one property of a coating by altering the polymer composition of the binder leads to a significant deterioration of other properties of the coating.

[0009] Although the polymer dispersions described in the aforementioned references have specific advantages in one or more states, they do not always possess a fully balanced set of application characteristics. Furthermore, they are based solely on monomers derived from fossil sources. Given the ongoing discussion regarding the impact of CO2 emissions, there is a need to reduce fossil carbon production from polymer latexes. [Summary of the Invention]

[0010] Therefore, one object of the present invention is to provide a polymer latex with sufficiently balanced application characteristics that allow the polymer latex to be used as a binder or co-binder in water-based coating compositions, specifically for external applications. However, the demand for fossil carbon should also be reduced.

[0011] Surprisingly, it has been found that polymer latexes based on acrylate monomers, methacrylate monomers, and / or monovinyl aromatic monomers (containing a certain amount of monomer M1 selected from isobutyl acrylate, isoamyl acrylate, and mixtures thereof) improve coating compositions, and specifically the coating properties of the coating compositions (i.e., the coating's resistance to whitening, water absorption, and flexibility), without deteriorating other properties (e.g., anti-blocking properties and surface hardness). Furthermore, monomer M1 can be obtained (at least with respect to its alkanoic portion) from biological sources, thereby reducing the fossil carbon requirement in the production of polymer latexes.

[0012] This invention relates to an aqueous polymer latex of a film-forming copolymer obtainable by aqueous emulsion polymerization of an olefinically unsaturated monomer M, wherein the monomer M comprises - at least one monomer M1, selected from isobutyl acrylate, 2-methylbutyl acrylate, and isoamyl acrylate, and mixtures thereof, based on the total amount of monomer M, from 20% to 90% by weight, particularly from 25% to 90% by weight, especially from 30% to 85% by weight; - at least one monomer M2, selected from ethyl acrylate, n-propyl acrylate, n-butyl acrylate, n-amyl acrylate, C6-C20-alkyl acrylate, and C5-C20-alkyl methacrylate, and mixtures thereof, based on the total amount of monomer M; Based on the total amount of monomer M, at least one monomer M3 is selected from 5% to 50% by weight, specifically 10% to 45% by weight, particularly 15% to 45% by weight, of tert-butyl acrylate, C1-C4-alkyl methacrylate, C5-C20-cycloalkyl acrylate, C5-C20-cycloalkyl methacrylate, C5-C20-cycloalkyl methacrylate, C5-C20-cycloalkyl methyl methacrylate, wherein the cycloalkyl group in the monomers mentioned above is mono-, di-, or tricyclic and wherein one or two CH2 moieties of the cycloalkyl group may be replaced by O, and wherein the cycloalkyl group may be unsubstituted or carry 1, 2, 3, or 4 methyl groups; and monovinyl aromatic monomers and mixtures thereof; Based on the total weight of monomer M, at least one monomer M4, selected from monoolefin unsaturated monomers having acidic groups, comprises 0.05 wt% to 4 wt%, preferably 0.05 wt% to 3.5 wt%, specifically 0.1 wt% to 4 wt% or 0.1 wt% to 3 wt%, particularly 0.2 wt% to 3 wt%, or 0.5 wt% to 3 wt%, or 0.5 wt% to 2 wt%. The total amount of monomers M1 and M2 based on the olefinic unsaturated monomer M is in the range of 45 wt% to 94.95 wt%, or 45 wt% to 94.9 wt%, or 45 wt% to 94.8 wt%, or 45 wt% to 94.5 wt%, particularly 50 wt% to 89.95 wt%, or 50 wt% to 94.9 wt%, or 50 wt% to 94.8 wt%, or 50 wt% to 94.5 wt%, especially 55 wt% to 84.95 wt%, or 55 wt% to 94.9 wt%, or 55 wt% to 94.8 wt%, or 55 wt% to 94.5 wt%, and the total amount of monomers M1, M2 and M3 based on the olefinic unsaturated monomer M is at least 90 wt%, particularly at least 92 wt%, and especially at least 95 wt%.

[0013] This invention also relates to a process for producing the aqueous polymer latex of this invention. The process includes aqueous emulsion polymerization of monomer M.

[0014] This invention also relates to the use of such polymer latexes as binders or co-binders in water-based coating compositions, specifically water-based compositions for wood coatings, such as water-based wood stain formulations, water-based wood paint formulations, and water-based clear coating formulations for wood surfaces; and also for water-based architectural coatings. This invention also relates to the use of the water-based polymer latexes described herein for improving the resistance of coatings obtained from water-based coating compositions described herein to water or moisture.

[0015] In addition, the present invention relates to a water-based coating composition containing: a) a binder polymer in the form of a water-based polymer latex as defined herein; and b) at least one other component that is commonly used in water-based coating compositions and is not a binder.

[0016] The present invention has several advantages. - The polymer latex is more stable and provides good and well-balanced application characteristics to water-based coating compositions. - Because the polymer latex contains a large amount of bioavailable monomer M1, it can significantly reduce the fossil carbon requirement, specifically by at least 10%, particularly by at least 15%, or even by at least 20%. - Water-based coating compositions containing the polymer latex of the present invention as a binder or co-binder have improved flexibility. - Water-based coating compositions containing the polymer latex of the present invention as a binder or co-binder exhibit excellent anti-blocking properties. - Water-based coating compositions containing the polymer latex of the present invention as a binder or co-binder have good weather resistance (specifically against moisture and UV radiation) and specifically improved resistance to whitening. - Water-based coating compositions containing the polymer latex of the present invention exhibit improved scrub resistance, improved gloss, improved thickening efficiency at high and low shear rates, reduced dust attraction, and comparable opacity, tackiness, and stain resistance. Due to its well-balanced application characteristics, polymer latex is particularly suitable as a binder or co-binder in water-based wood coatings, and has beneficial properties in water-based primers and topcoat formulations.

Implementation Method

[0017] Herein and throughout the specification, the term "(meth)acryl" includes acrylonitrile and methacrylonitrile. Therefore, the term "(meth)acrylate" includes acrylate and methacrylate, and the term "(meth)acrylamine" includes acrylamine and methacrylamine.

[0018] Herein and throughout the specification, the term "water-based coating composition" means a liquid water-based coating composition containing an amount of water sufficient to achieve flowability as a continuous phase.

[0019] The terms “wt.-%” and “weight% (% bw)” are used synonymously throughout this specification.

[0020] Herein and throughout the specification, the term "pphm" means the number of parts by weight per 100 parts of monomer and the relative amount (in weight %) of a substance based on the total amount of monomer M.

[0021] Herein and throughout the specification, the term "olefinic unsaturated monomer" should be understood as a monomer having at least one C=C double bond (e.g., 1, 2, 3, or 4 C=C double bonds) that is free radical polymerizable, i.e., it polymerizes under the conditions of an aqueous free radical emulsion polymerization process to obtain a polymer with a carbon atom backbone. Herein and throughout the specification, the term "monoolefinic unsaturated" should be understood as a monomer having a single C=C double bond that is readily free radical polymerizable under the conditions of an aqueous free radical emulsion polymerization process.

[0022] Herein and throughout the specification, the terms "ethoxylation" and "polyethoxylation" are used synonymously and refer to compounds having oligo- or polyoxyethylene groups formed from repeating units O-CH2CH2. In this context, the term "degree of ethoxylation" refers to the average number of repeating units O-CH2CH2 in such compounds.

[0023] Herein and throughout the specification, the term “nonionic” in the context of compounds, especially monomers, means that the individual compounds do not have any ionic functional groups or any functional groups that can be converted into ionic groups by protonation or deprotonation.

[0024] Herein and throughout the specification, the prefixes Cn-Cm used in conjunction with the compound or molecular part each indicate the range of possible numbers of carbon atoms that the molecular part or compound may have. The term "C1-Cn alkyl" names a group of straight-chain or branched saturated hydrocarbon groups having 1 to n carbon atoms. The term "Cn / Cm alkyl" names a mixture of two alkyl groups, one having n carbon atoms and the other having m carbon atoms.

[0025] For example, the term C1-C20 alkyl nomenclature has one group of straight-chain or branched saturated hydrocarbon groups with 1 to 20 carbon atoms, while the term C1-C4 alkyl nomenclature has one group of straight-chain or branched saturated hydrocarbon groups with 1 to 4 carbon atoms, and the term C5-C20 alkyl nomenclature has one group of straight-chain or branched saturated hydrocarbon groups with 5 to 20 carbon atoms. Examples of alkyl groups include (but are not limited to) methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, isobutyl, tributyl, 2-methylpropyl (isopropyl), 1,1-dimethylethyl (tributyl), pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-Trimethylpropyl, 1-Ethyl-1-methylpropyl, 1-Ethyl-2-methylpropyl, n-Heptyl, 2-Heptyl, n-Octyl, 2-Octyl, 2-Ethylhexyl, Nonyl, Isononyl, Decyl, Undecyl, Dodecyl, Tridecyl, Isotridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecanyl, Octadecanyl, Nonadecanyl, Eicosyl, Dodecyl, Dodecyl, Isotridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Octadecanyl, Nonadecanyl, Eicosyl, Dodecyl, Dodecyl, and Dodecyl, and their isomers, and specifically mixtures of isomers (e.g., "Isononyl", "Isonodecanyl"). Examples of C1-C4-alkyl are (e.g.) methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, or 1,1-dimethylethyl.

[0026] As used herein, the term "C5-C20-cycloalkyl" refers to a mono- or bicyclic cycloaliphatic group that is unsubstituted or substituted with 1, 2, 3, or 4 methyl groups, wherein the total number of carbon atoms in a C5-C20-cycloalkyl group is 5 to 20. Examples of C5-C20-cycloalkyl groups include (but are not limited to) cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclohexadecyl, norcamphenyl (= bicyclo[2.2.1]heptyl) and isocamphenyl (= 1,7,7-trimethylbicyclo[2.2.1]heptyl). In a cycloalkyl group, one or two CH2 groups may be substituted by non-adjacent oxygen ring atoms to produce a heterocyclic aliphatic group. Examples of such groups include (but are not limited to) oxapentyl-2-yl, oxapentyl-3-yl, oxan-2-yl, oxan-3-yl, oxan-4-yl, 1,3-dioxapentyl-2-yl, 1,3-dioxapentyl-4-yl, 2,2-dimethyl-1,3-dioxapentyl-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, and 2,2-dimethyl-1,3-dioxan-5-yl.

[0027] As used herein, the term “C5-C20-cycloalkylmethyl” refers to a C5-C20-cycloalkyl group as defined herein, which is bound via a methylene group.

[0028] According to the present invention, monomer M comprises at least one monomer M1 selected from isobutyl acrylate, 2-methylbutyl acrylate, and isoamyl acrylate and mixtures thereof. Isoamyl acrylate is also known as isopentyl acrylate or 3-methylbutyl acrylate. 2-methylbutyl acrylate is an anisotropic compound and thus can exist in racemic form or in a non-racemic mixture (including an excess of one enantiomer). According to the present invention, monomer M1 comprises non-racemic 2-methylbutyl acrylate and racemic 2-methylbutyl acrylate.

[0029] In embodiments of a particular group, based on the total amount of monomer M1, monomer M1 comprises at least 50% by weight, specifically at least 80% by weight, and especially at least 90% by weight of isobutyl acrylate. In particular, monomer M1 is isobutyl acrylate.

[0030] In embodiments of other specific groups, monomer M1 comprises at least 50% by weight, specifically at least 80% by weight, and especially at least 90% by weight, of isoamyl acrylate, based on the total amount of monomer M1. In embodiments of this specific group, monomer M1 is particularly isoamyl acrylate.

[0031] In embodiments of other specific groups, monomer M1 comprises at least 50% by weight, and specifically at least 80% by weight, of 2-methyl butyl acrylate, based on the total amount of monomer M1. In embodiments of this specific group, monomer M1 is particularly 2-methyl butyl acrylate.

[0032] In embodiments of other specific groups, monomer M1 comprises a mixture of isoamyl acrylate and 2-methylbutyl acrylate (in an amount of at least 50% by weight, specifically at least 80% based on the total amount of monomer M1) and, where applicable, at most 50% by weight, particularly not more than 20% by weight (based on the total amount of monomer M1) of isobutyl acrylate. In embodiments of this specific group, the monomer molar ratio of 3-methylbutyl acrylate to 2-methylbutyl acrylate is specifically in the range of 1:1 to 10:1.

[0033] Isobutyl acrylate, 2-methylbutyl acrylate and isoamyl acrylate are usually produced by esterifying acrylate with isobutanol (2-methylpropane-1-ol), 2-methylbutanol or isoamyl alcohol (3-methylbutane-1-ol), or transesterifying methyl acrylate or ethyl acrylate with isobutanol (2-methylpropane-1-ol), 2-methylbutane-1-ol or isoamyl alcohol (3-methylbutane-1-ol).

[0034] Isobutanol, 2-methylbutanol, and isoamyl alcohol, and mixtures thereof, can be produced on a large scale from various renewable raw materials (including corn, wheat, sorghum, barley, and sugarcane), specifically from cellulose raw materials contained therein, and thus from biological or renewable raw materials. Therefore, the inclusion of monomer M1 in the polymer latex significantly increases the amount of biochar in the polymer latex, thereby reducing the demand for fossil carbon and (therefore) the CO2 demand generated by the polymer latex. Specifically, fermentation can produce a mixture comprising various alkanols, from which isobutanol, 2-methylbutane-1-ol, and 3-methylbutane-1-ol can be separated by conventional techniques (e.g., fractionation). Thus, pure alcohols (purity > 90%) or mixtures containing at least two alcohols selected from the group consisting of isobutanol, 2-methylbutane-1-ol, and 3-methylbutane-1-ol (total amount at least 80%, specifically at least 90%) can be obtained. For example, esterification or transesterification can be performed using a mixture comprising at least 80% by weight of 2-methylbutanol and 3-methylbutanol and up to 20% by weight of isobutanol. In this mixture, the molar ratio of 3-methylbutanol to 2-methylbutane-1-ol can vary, for example from 1:10 to 10:1 and specifically in the range of 1:1 to 10:1.

[0035] Acrylic acid for esterification can be obtained from fossil sources according to standard procedures. Acrylic acid can also be prepared from renewable raw materials, for example, according to WO 2006 / 092272 or DE 10 2006 039 203 A or EP 2 922 580.

[0036] At least a portion of the segregated material can also be used to synthesize the bio-based monomer M1 from renewable raw materials using a mass balance method. Therefore, in addition to fossil fuels, renewable raw materials (e.g., bio-naphtha, as described in, for example, EP 2 290 045 A1 or EP 2 290 034 A1) also enter the chemical production system (e.g., a steam cracker). The renewable raw materials are converted into products belonging to the chemical value chain, such as acrylic acid, isobutanol, isoamyl alcohol, or 2-methylbutanol, or isobutyl acrylate, isoamyl acrylate, or 2-methylbutyl acrylate. The content of renewable materials in these products is defined and allocated to these products using a mass balance method.

[0037] Therefore, one specific embodiment of the invention relates to a polymer latex as defined herein, wherein the carbon atoms of at least the isobutyl, 2-methylbutyl, and isopentyl groups in monomer M1 are of biological origin, i.e., at least partially derived from biocarbon. Specifically, the isobutanol, 2-methylbutane-1-ol, and isopentyl alcohol used to generate monomer M1 preferably have a biocarbon content of at least 90 mol-%, based on the total carbon atoms in isobutanol, 2-methylpentanol, and isopentyl alcohol, respectively. This content is advantageously higher, specifically greater than or equal to 95 mol-%, preferably greater than or equal to 98 mol-%, and advantageously equal to 100 mol-%. Similarly, acrylic acid can be generated from renewable materials. However, to date, acrylic acid derived from biomaterials has not been utilized on a large scale. Therefore, based on the total carbon atoms of isobutyl acrylate, 2-methylbutyl acrylate, and isoamyl acrylate, respectively, monomer M1 preferably has a bio-carbon content of at least 51 mol-%, specifically at least 54 mol-%, and particularly at least 57 mol-%. By using monomer M1 that is at least partially of biological origin, the fossil carbon requirement in polymer latex can be significantly reduced. Specifically, a bio-carbon content of at least 10 mol-%, specifically at least 15 mol-%, or at least 20 mol-%, or higher (e.g., 30 mol-%, or 40 mol-%, or higher) can be achieved.

[0038] The term "biocarbon" indicates that the carbon is of biological origin and derived from biomaterials / renewable resources. The content of biocarbon and the content of biomaterials are expressions indicating the same value. Renewable source materials or biomaterials are organic materials in which the carbon originates from the most recent (on a human scale) CO2 fixed by atmospheric photosynthesis. Biomaterials (100% naturally derived carbon) have an isotopic ratio of 14C / 12C greater than 10⁻¹², typically about 1.2 × 10⁻¹², while this ratio is zero in fossil materials. In fact, isotope 14C is formed in the atmosphere and then integrated through photosynthesis over a period of at most several decades. The half-life of 14C is 5,730 years. Therefore, materials derived from photosynthesis (i.e., typical plants) must have the highest content of isotope 14C. The content of biomaterials or biocarbon can be determined according to standard ASTM D 6866-12, method B (ASTM D 6866-06) and ASTM D 7026 (ASTM D 7026-04).

[0039] In addition to monomer M1, monomer M of the polymer forming the latex may also include one or more monomers M2 as defined above.

[0040] Suitable monomers M2 are selected from the following groups: - ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate; - C6-C20 alkyl acrylates, including (but not limited to) hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, isodecyl acrylate, 2-propylheptyl acrylate, lauryl acrylate, C12 / C14 alkyl acrylates, C12-C15 alkyl acrylates, isotridecyl acrylate, C16 / C18 alkyl acrylates, and stearyl acrylate; - C5-C20 alkyl methacrylates, including (but not limited to) n-pentyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, n-decyl methacrylate, 2-propylheptyl methacrylate, lauryl methacrylate, C12 / C14 alkyl methacrylates, C12-C15 alkyl methacrylates, isotridecyl methacrylate, C16 / C18 alkyl methacrylates, and stearyl methacrylate; - and mixtures thereof.

[0041] The preferred monomer M2 system is selected from the group consisting of: ethyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate and mixtures thereof (e.g., mixtures of butyl acrylate and 2-ethylhexyl acrylate, or mixtures of butyl acrylate and ethyl acrylate, or mixtures of ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate and mixtures thereof).

[0042] The preferred monomer M2 series is selected from the group consisting of: n-butyl acrylate and 2-ethylhexyl acrylate and mixtures thereof.

[0043] Suitable monomers M3 are selected from the following group of compositions: - C1-C4 alkyl methacrylates, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, dibutyl methacrylate, isobutyl methacrylate and tributyl methacrylate; - tributyl acrylate; - C5-C20 cycloalkyl methacrylates, including (but not limited to) cyclohexyl acrylate, cyclohexyl methacrylate, norborneol acrylate, norborneol methacrylate, isoborneol acrylate, isoborneol methacrylate, 1,3-dioxane-5-yl acrylate, 1,3-dioxane-5-yl methacrylate, 2,2-dimethyl-1,3-dioxane-5-yl acrylate, 2,2-dimethyl-1,3-dioxane-5-yl methacrylate; - (Meth)acrylate C5-C20 cycloalkyl methyl esters, including (but not limited to) cyclohexyl methyl acrylate, cyclohexyl methyl methacrylate, 1,3-dioxapentane-4-yl-methyl acrylate, 1,3-dioxapentane-4-yl-methyl methacrylate, 2,2-dimethyl-1,3-dioxapentane-4-yl-methyl acrylate, 2,2-dimethyl-1,3-dioxapentane-4-yl-methyl methacrylate, oxapentane-2-yl-methyl acrylate (tetrahydrofurfuryl acrylate), and oxapentane-2-yl-methyl methacrylate (tetrahydrofurfuryl methacrylate); - monovinyl aromatic monomers, such as styrene, 2-methylstyrene, 4-methylstyrene; and mixtures thereof.

[0044] The preferred monomer M3 is selected from the group consisting of: - C1-C4-alkyl methacrylates, specifically methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and tributyl methacrylate; - tributyl acrylate; - cyclohexyl methacrylate, isocamphenyl methacrylate, isocamphenyl methacrylate; - styrene; and mixtures thereof.

[0045] The preferred monomer M3 series is selected from the group consisting of: - methyl methacrylate, n-butyl methacrylate; - tributyl acrylate; - cyclohexyl methacrylate, isocamphenyl methacrylate; - styrene; and mixtures thereof.

[0046] Specifically, based on the total amount of monomer M3 in monomer M, monomer M3 comprises methyl methacrylate in an amount of at least 50% by weight, specifically at least 80% by weight or 100% by weight. More specifically, monomer M3 is selected from the group consisting of methyl methacrylate and combinations of methyl methacrylate with n-butyl methacrylate, tributyl acrylate, cyclohexyl methacrylate, isoborneol methacrylate or styrene.

[0047] Suitable monomer M4 includes (but is not limited to): - Monoalkenyl unsaturated monocarboxylic acids having 3 to 6 carbon atoms, such as acrylic acid, methacrylic acid, crotonic acid, 2-ethylacrylic acid, 2-propylacrylic acid, 2-acryloyloxyacetic acid, and 2-methacryloyloxyacetic acid; - Monoalkenyl unsaturated dicarboxylic acids having 4 to 6 carbon atoms, such as itaconic acid, citraconic acid, and fumaric acid; - Half-esters of monoalkenyl unsaturated dicarboxylic acids having 4 to 6 carbon atoms with C1-C4 alkanols (e.g., methanol or ethanol), such as itaconic acid, citraconic acid, maleic acid, or fumaric acid with methanol or ethanol; - Monoalkenyl unsaturated sulfonic acids, such as vinylsulfonic acid, allylsulfonic acid, styrenesulfonic acid, and 2-acrylamino-2-methylpropanesulfonic acid; Monoalkene unsaturated phosphonic acids, such as vinylphosphonic acid, allylphosphonic acid, styrenephosphonic acid, and 2-acrylamino-2-methylpropanephosphonic acid; - Monoalkene unsaturated phosphates, such as monophosphates of hydroxyalkyl acrylates, monophosphates of hydroxyalkyl methacrylates, monophosphates of alkoxylated hydroxyalkyl acrylates and monophosphates of alkoxylated hydroxyalkyl methacrylates, specifically monophosphates of hydroxyethyl acrylates, hydroxypropyl acrylates or hydroxybutyl acrylates, monophosphates of hydroxyethyl methacrylates, hydroxypropyl methacrylates or hydroxybutyl methacrylates, monophosphates of ethoxylated hydroxy-C2-C4-alkyl acrylates, monophosphates of propoxylated hydroxy-C2-C4-alkyl acrylates, monophosphates of ethoxylated hydroxy-C2-C4-alkyl methacrylates and monophosphates of propoxylated hydroxy-C2-C4-alkyl methacrylates.

[0048] The monomer M4 mentioned above may exist in its acidic form or in its salt form, specifically in its alkali metal salt or ammonium salt form.

[0049] Among the monomers M4 mentioned above, preferred ones are monoalkenyl unsaturated monocarboxylic acids and monoalkenyl unsaturated dicarboxylic acids. More preferably, they are acrylic acid, methacrylic acid, itaconic acid, and mixtures thereof. Even more preferably, they are monoalkenyl unsaturated monocarboxylic acids, specifically acrylic acid, methacrylic acid, and mixtures thereof. In certain group of embodiments, monomer M4 includes methacrylic acid. In particular, monomer M4 is methacrylic acid or a mixture of acrylic acid and methacrylic acid.

[0050] Based on the total weight of monomer M, the total amount of monomer M4 is 0.05 wt% to 4 wt% or 0.1 wt% to 4 wt%, preferably 0.05 wt% to 3.5 wt%, specifically 0.1 wt% to 3 wt%, especially 0.2 wt% to 3 wt% or 0.5 wt% to 3 wt% or 0.5 wt% to 2 wt%.

[0051] Preferably, monomer M comprises: - 20% to 90% by weight, particularly 25% to 90% by weight, especially 30% to 85% by weight of monomer M, having at least 50 mol-% biochar, based on the total amount of monomer M; - at least one monomer M2, 0% to 55% by weight, particularly 0% to 50% by weight, especially 0% to 40% by weight, based on the total amount of monomer M, which is selected from ethyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, 2-propylheptaacrylate and mixtures thereof (e.g., mixtures of butyl acrylate and 2-ethylhexyl acrylate, or mixtures of butyl acrylate and ethyl acrylate, or mixtures of ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate and mixtures thereof); - Based on the total amount of monomer M, at least one monomer M3 comprising 5% to 50%, specifically 10% to 45% by weight, particularly 15% to 45% by weight, of which is selected from tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isoborneol acrylate, isoborneol methacrylate, and styrene and mixtures thereof; - Based on the total weight of monomer M, at least one monomer M4 comprising 0.05% to 4% by weight or 0.1% to 4% by weight, preferably 0.05% to 3.5% by weight, specifically 0.1% to 3% by weight, particularly 0.2% to 3% by weight or 0.5% to 3% by weight or 0.5% to 2% by weight, of which is selected from monoalkenyl unsaturated monocarboxylic acids and monoalkenyl unsaturated dicarboxylic acids and mixtures thereof. The total amount of monomers M1 and M2 based on the olefinic unsaturated monomer M is in the range of 45 wt% to 94.95 wt%, or 45 wt% to 94.9 wt%, or 45 wt% to 94.8 wt%, or 45 wt% to 94.5 wt%, particularly 50 wt% to 89.95 wt%, or 50 wt% to 94.9 wt%, or 50 wt% to 94.8 wt%, or 50 wt% to 94.5 wt%, especially 55 wt% to 84.95 wt%, or 55 wt% to 94.9 wt%, or 55 wt% to 94.8 wt%, or 55 wt% to 94.5 wt%, and the total amount of monomers M1, M2 and M3 based on the olefinic unsaturated monomer M is at least 90 wt%, particularly at least 92 wt%, and especially at least 95 wt%.

[0052] Specifically, monomer M comprises: - 20% to 90% by weight, particularly 25% to 90% by weight, especially 30% to 85% by weight of monomer M, having at least 50 mol-% biochar, based on the total amount of monomer M; - at least one monomer M2, selected from n-butyl acrylate and 2-ethylhexyl acrylate, and mixtures thereof, based on the total amount of monomer M; - at least one monomer M3, selected from 5% to 50% by weight, particularly 10% to 45% by weight, especially 15% to 45% by weight of monomer M, based on the total amount of monomer M; - methyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, isoborneol methacrylate, and styrene, and mixtures thereof; Based on the total weight of monomer M, at least one monomer M4, selected from monoolefinic unsaturated monocarboxylic acids, comprises 0.05 wt% to 4 wt% or 0.1 wt% to 4 wt%, preferably 0.05 wt% to 3.5 wt%, specifically 0.1 wt% to 3 wt%, particularly 0.2 wt% to 3 wt%, or 0.5 wt% to 3 wt%, or 0.5 wt% to 2 wt%. The total amount of monomers M1 and M2 based on the olefinic unsaturated monomer M is in the range of 45 wt% to 94.95 wt%, or 45 wt% to 94.9 wt%, or 45 wt% to 94.8 wt%, or 45 wt% to 94.5 wt%, specifically 50 wt% to 89.95 wt%, or 50 wt% to 94.9 wt%, or 50 wt% to 94.8 wt%, or 50 wt% to 94.5 wt%, particularly 55 wt% to 84.95 wt%, or 55 wt% to 94.9 wt%, or 55 wt% to 94.8 wt%, or 55 wt% to 94.5 wt%, and the total amount of monomers M1, M2 and M3 based on the olefinic unsaturated monomer M is at least 90 wt%, specifically at least 95 wt%.

[0053] Even more preferably, monomer M comprises: - 20% to 90% by weight, particularly 25% to 90% by weight, especially 30% to 85% by weight of monomer M, having at least 50 mol-% biochar; - 0% to 55% by weight, particularly 0% to 50% by weight, especially 0% to 40% by weight of at least one monomer M2, selected from n-butyl acrylate and 2-ethylhexyl acrylate and mixtures of n-butyl acrylate and 2-ethylhexyl acrylate; - 5% to 50% by weight, particularly 10% to 45% by weight, especially 15% to 45% by weight of monomer M, selected from methyl methacrylate and combinations of methyl methacrylate with at least one other monomer M3 selected from tributyl acrylate, n-butyl methacrylate, cyclohexyl methacrylate, isoborneol methacrylate and styrene; - Based on the total weight of monomer M, at least one monomer M4, selected from acrylic acid, methacrylic acid, itaconic acid, and mixtures thereof, comprises 0.05 wt% to 4 wt% or 0.1 wt% to 4 wt%, preferably 0.05 wt% to 3.5 wt%, specifically 0.1 wt% to 3 wt%, particularly 0.2 wt% to 3 wt%, or 0.5 wt% to 3 wt%, or 0.5 wt% to 2 wt%. The total amount of monomers M1 and M2 based on the olefinic unsaturated monomer M is in the range of 45 wt% to 94.95 wt%, or 45 wt% to 94.9 wt%, or 45 wt% to 94.8 wt%, or 45 wt% to 94.5 wt%, specifically 50 wt% to 89.95 wt%, or 50 wt% to 94.9 wt%, or 50 wt% to 94.8 wt%, or 50 wt% to 94.5 wt%, particularly 55 wt% to 84.95 wt%, or 55 wt% to 94.9 wt%, or 55 wt% to 94.8 wt%, or 55 wt% to 94.5 wt%, and the total amount of monomers M1, M2 and M3 based on the olefinic unsaturated monomer M is at least 90 wt%, specifically at least 95 wt%.

[0054] In particular, monomer M comprises: - 20% to 90% by weight, specifically 25% to 90% by weight, particularly 30% to 85% by weight, of monomer M1 having at least 50 mol-% biochar, based on the total amount of monomer M; - at least one monomer M2, selected from n-butyl acrylate and 2-ethylhexyl acrylate and mixtures of n-butyl acrylate and 2-ethylhexyl acrylate, based on the total amount of monomer M; - 5% to 50% by weight, specifically 10% to 45% by weight, particularly 15% to 45% by weight, of methyl methacrylate (as monomer M3), based on the total amount of monomer M; Based on the total weight of monomer M, at least one monomer M4, selected from methacrylic acid and mixtures of acrylic acid and methacrylic acid, comprises 0.05 wt% to 4 wt% or 0.1 wt% to 4 wt%, preferably 0.05 wt% to 3.5 wt%, specifically 0.1 wt% to 3 wt%, particularly 0.2 wt% to 3 wt%, or 0.5 wt% to 3 wt%, or 0.5 wt% to 2 wt%. The total amount of monomers M1 and M2 based on the olefinic unsaturated monomer M is in the range of 45 wt% to 94.95 wt%, or 45 wt% to 94.9 wt%, or 45 wt% to 94.8 wt%, or 45 wt% to 94.5 wt%, specifically 50 wt% to 89.95 wt%, or 50 wt% to 94.9 wt%, or 50 wt% to 94.8 wt%, or 50 wt% to 94.5 wt%, particularly 55 wt% to 84.95 wt%, or 55 wt% to 94.9 wt%, or 55 wt% to 94.8 wt%, or 55 wt% to 94.5 wt%, and the total amount of monomers M1, M2 and M3 based on the olefinic unsaturated monomer M is at least 90 wt%, specifically at least 95 wt%.

[0055] In specific embodiment group 1, monomer M comprises: - 20% to 90% by weight, specifically 25% to 90% by weight, particularly 30% to 85% by weight of isobutyl acrylate, specifically having at least 50 mol-% biochar (as monomer M1), based on the total amount of monomer M; - at least one monomer M2, 0% to 55% by weight, specifically 0% to 50% by weight, particularly 0% to 40% by weight, based on the total amount of monomer M, which is selected from n-ethyl acrylate, n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, 2-propylheptaacrylate and mixtures thereof (e.g., mixtures of n-butyl acrylate and 2-ethylhexyl acrylate or mixtures of n-butyl acrylate and ethyl acrylate or mixtures of ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate and mixtures thereof); - Based on the total amount of monomer M, at least one monomer M3 comprising 5% to 50%, specifically 10% to 45% by weight, particularly 15% to 45% by weight, of which is selected from tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isoborneol acrylate, isoborneol methacrylate, and styrene and mixtures thereof; - Based on the total weight of monomer M, at least one monomer M4 comprising 0.05% to 4% by weight or 0.1% to 4% by weight, preferably 0.05% to 3.5% by weight, specifically 0.1% to 3% by weight, particularly 0.2% to 3% by weight or 0.5% to 3% by weight or 0.5% to 2% by weight, of which is selected from monoalkenyl unsaturated monocarboxylic acids and monoalkenyl unsaturated dicarboxylic acids and mixtures thereof. The total amount of monomers M1 and M2 based on the olefinic unsaturated monomer M is in the range of 45 wt% to 94.95 wt%, or 45 wt% to 94.9 wt%, or 45 wt% to 94.8 wt%, or 45 wt% to 94.5 wt%, particularly 50 wt% to 89.95 wt%, or 50 wt% to 94.9 wt%, or 50 wt% to 94.8 wt%, or 50 wt% to 94.5 wt%, especially 55 wt% to 84.95 wt%, or 55 wt% to 94.9 wt%, or 55 wt% to 94.8 wt%, or 55 wt% to 94.5 wt%, and the total amount of monomers M1, M2 and M3 based on the olefinic unsaturated monomer M is at least 90 wt%, particularly at least 92 wt%, and especially at least 95 wt%.

[0056] In specific embodiment group 1, monomer M preferably includes: - 20% to 90% by weight, specifically 25% to 90% by weight, particularly 30% to 85% by weight of isobutyl acrylate, specifically having at least 50 mol-% biochar (as monomer M1), based on the total amount of monomer M; - at least one monomer M2, selected from n-butyl acrylate and 2-ethylhexyl acrylate, and mixtures of n-butyl acrylate and 2-ethylhexyl acrylate, based on the total amount of monomer M; - at least one monomer M3, selected from 5% to 50% by weight, specifically 10% to 45% by weight, particularly 15% to 45% by weight of tributyl acrylate, methyl methacrylate, n-butyl methacrylate, cyclohexyl methacrylate, isoborneol methacrylate, and styrene, and mixtures thereof, based on the total amount of monomer M; Based on the total weight of monomer M, at least one monomer M4, selected from monoolefinic unsaturated monocarboxylic acids, comprises 0.05 wt% to 4 wt% or 0.1 wt% to 4 wt%, preferably 0.05 wt% to 3.5 wt%, specifically 0.1 wt% to 3 wt%, particularly 0.2 wt% to 3 wt%, or 0.5 wt% to 3 wt%, or 0.5 wt% to 2 wt%. The total amount of monomers M1 and M2 based on the olefinic unsaturated monomer M is in the range of 45 wt% to 94.95 wt%, or 45 wt% to 94.9 wt%, or 45 wt% to 94.8 wt%, or 45 wt% to 94.5 wt%, particularly 50 wt% to 89.95 wt%, or 50 wt% to 94.9 wt%, or 50 wt% to 94.8 wt%, or 50 wt% to 94.5 wt%, especially 55 wt% to 84.95 wt%, or 55 wt% to 94.9 wt%, or 55 wt% to 94.8 wt%, or 55 wt% to 94.5 wt%, and the total amount of monomers M1, M2 and M3 based on the olefinic unsaturated monomer M is at least 90 wt%, particularly at least 95 wt% (Example Group 1a).

[0057] In specific embodiment group 1, monomer M preferably comprises: - 20% to 90% by weight, specifically 25% to 90% by weight, particularly 30% to 85% by weight of isobutyl acrylate, specifically having at least 50 mol-% biochar (as monomer M1), based on the total amount of monomer M; - at least one monomer M2, selected from n-butyl acrylate and 2-ethylhexyl acrylate, specifically 0% to 50% by weight, particularly 0% to 40% by weight, based on the total amount of monomer M, which is selected from n-butyl acrylate and 2-ethylhexyl acrylate and mixtures of n-butyl acrylate and 2-ethylhexyl acrylate; - Based on the total amount of monomer M, 5% to 50% by weight, particularly 10% to 45% by weight, especially 15% to 45% by weight of monomer M3, which is selected from methyl methacrylate and combinations of methyl methacrylate with at least one other monomer M3 selected from tributyl acrylate, n-butyl methacrylate, cyclohexyl methacrylate, isoborneol methacrylate and styrene; - Based on the total weight of monomer M, 0.05% to 4% by weight or 0.1% to 4% by weight, preferably 0.05% to 3.5% by weight, particularly 0.1% to 3% by weight, especially 0.2% to 3% by weight or 0.5% to 3% by weight or 0.5% to 2% by weight of at least one monomer M4, which is selected from acrylic acid, methacrylic acid, itaconic acid and mixtures thereof. The total amount of monomers M1 and M2 based on the olefinic unsaturated monomer M is in the range of 45 wt% to 94.95 wt%, or 45 wt% to 94.9 wt%, or 45 wt% to 94.8 wt%, or 45 wt% to 94.5 wt%, particularly 50 wt% to 89.95 wt%, or 50 wt% to 94.9 wt%, or 50 wt% to 94.8 wt%, or 50 wt% to 94.5 wt%, especially 55 wt% to 84.95 wt%, or 55 wt% to 94.9 wt%, or 55 wt% to 94.8 wt%, or 55 wt% to 94.5 wt%, and the total amount of monomers M1, M2 and M3 based on the olefinic unsaturated monomer M is at least 90 wt%, particularly at least 95 wt% (Example Group 1b).

[0058] In specific embodiment group 1, monomer M particularly includes: - 20% to 90% by weight, specifically 25% to 90% by weight, particularly 30% to 85% by weight of isobutyl acrylate, specifically having at least 50 mol-% biochar (as monomer M1), based on the total amount of monomer M; - at least one monomer M2, selected from n-butyl acrylate and 2-ethylhexyl acrylate, and mixtures of n-butyl acrylate and 2-ethylhexyl acrylate, based on the total amount of monomer M; - 5% to 50% by weight, specifically 10% to 45% by weight, particularly 15% to 45% by weight of methyl methacrylate (as monomer M3), based on the total amount of monomer M; Based on the total weight of monomer M, at least one monomer M4, selected from methacrylic acid and mixtures of acrylic acid and methacrylic acid, comprises 0.05 wt% to 4 wt% or 0.1 wt% to 4 wt%, preferably 0.05 wt% to 3.5 wt%, specifically 0.1 wt% to 3 wt%, particularly 0.2 wt% to 3 wt%, or 0.5 wt% to 3 wt%, or 0.5 wt% to 2 wt%. The total amount of monomers M1 and M2 based on the olefinic unsaturated monomer M is in the range of 45 wt% to 94.95 wt%, or 45 wt% to 94.9 wt%, or 45 wt% to 94.8 wt%, or 45 wt% to 94.5 wt%, particularly 50 wt% to 89.95 wt%, or 50 wt% to 94.9 wt%, or 50 wt% to 94.8 wt%, or 50 wt% to 94.5 wt%, especially 55 wt% to 84.95 wt%, or 55 wt% to 94.9 wt%, or 55 wt% to 94.8 wt%, or 55 wt% to 94.5 wt%, and the total amount of monomers M1, M2 and M3 based on the olefinic unsaturated monomer M is at least 90 wt%, particularly at least 95 wt% (Example Group 1c).

[0059] In Specific Embodiment Group 2, the types and amounts of monomers M1, M2, M3 and M4 are as defined in Specific Embodiment Group 1, except that monomer M1 is isoamyl acrylate instead of isobutyl acrylate.

[0060] In the specific embodiment group 2, the preferred embodiment is embodiment 2a, wherein the type and amount of monomers M1, M2, M3 and M4 are as defined in the specific embodiment group 1a, except that monomer M1 is isoamyl acrylate instead of isobutyl acrylate.

[0061] In particular, in the specific embodiment group 2, the preferred embodiment is embodiment 2b, wherein the type and amount of monomers M1, M2, M3 and M4 are as defined in the more preferred embodiment group 1b, except that monomer M1 is isoamyl acrylate instead of isobutyl acrylate.

[0062] In the specific embodiment group 2, the preferred embodiment is embodiment 2c, wherein the type and amount of monomers M1, M2, M3 and M4 are as defined in the specific embodiment group 1c, except that monomer M1 is isoamyl acrylate instead of isobutyl acrylate.

[0063] In Specific Embodiment Group 3, the types and amounts of monomers M1, M2, M3 and M4 are as defined in Specific Embodiment Group 1, except that monomer M1 is a mixture of at least 80% by weight (based on the total amount of monomer M1) isoamyl acrylate and 2-methyl butyl acrylate and, where appropriate, up to 20% isobutyl acrylate, instead of isobutyl acrylate.

[0064] In the specific embodiment group 3, the preferred embodiment is embodiment 3a, wherein the type and amount of monomers M1, M2, M3 and M4 are as defined in the specific embodiment group 1a, except that monomer M1 is a mixture of at least 80% by weight (based on the total amount of monomer M1) isoamyl acrylate and 2-methyl butyl acrylate and, where appropriate, up to 20% isobutyl acrylate instead of isobutyl acrylate.

[0065] In particular, in the specific embodiment group 3, the preferred embodiment is embodiment 3b, wherein the type and amount of monomers M1, M2, M3 and M4 are as defined in the more preferred embodiment group 1b, except that monomer M1 is a mixture of at least 80% by weight (based on the total amount of monomer M1) of isoamyl acrylate and 2-methyl butyl acrylate and, where appropriate, up to 20% of isobutyl acrylate, instead of isobutyl acrylate.

[0066] In the specific embodiment group 3, the preferred embodiment is embodiment 3c, wherein the type and amount of monomers M1, M2, M3 and M4 are as defined in the specific embodiment group 1c, except that monomer M1 is a mixture of at least 80% by weight (based on the total amount of monomer M1) of isoamyl acrylate and 2-methyl butyl acrylate and, where appropriate, up to 20% of isobutyl acrylate, instead of isobutyl acrylate.

[0067] In addition to monomers M1, M2, M3 and M4 mentioned above, monomer M may also include one or more other monomers different from those mentioned above. Suitable monomers M different from monomers M1, M2, M3 and M4 include (but are not limited to): - Monomer M5, which is selected from monoolefin unsaturated nonionic monomers with a solubility of at least 60 g / L in deionized water at 20°C and 1 bar; - Monomer M6, which is selected from monoolefin unsaturated nonionic monomers having silane functional groups or epoxy groups; - Monomer M7, which is selected from polyolefin unsaturated monomers, that is, monomers having at least two non-conjugated olefin unsaturated double bonds; - Monomer M8, which is selected from monoolefin unsaturated copolymerizable UV-initiators.

[0068] Suitable nonionic monoolefin unsaturated monomers M5 series (for example) having functional groups selected from hydroxyalkyl, specifically hydroxy-C2-C4-alkyl, primary carboxylamine, urea and ketone groups.

[0069] Based on the total amount of monomer M, the total amount of monomer M5 generally does not exceed 10% by weight, specifically 7% by weight. Specifically, based on the total weight of monomer M, the total amount of monomer M5 (if present) is generally 0.05% by weight to 10% by weight, specifically 0.1% by weight to 7% by weight, particularly 0.1% by weight to 5% by weight, or 0.1% by weight to 4% by weight, or 0.5% by weight to 3% by weight, or 1% by weight to 3% by weight.

[0070] Examples of monomer M5 having a methacrylamide group (hereinafter, monomer M5a) include (but are not limited to) primary amides (e.g., acrylamide and methacrylamide) of monoalkenyl unsaturated monocarboxylic acids having 3 to 6 carbon atoms and C1-C4-alkylamides (e.g., N-methacrylamide, N-ethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, N-butylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-isopropylmethacrylamide, and N-butylmethacrylamide) of monoalkenyl unsaturated monocarboxylic acids having 3 to 6 carbon atoms. Preferably, monomer M5a is selected from acrylamide and methacrylamide.

[0071] Examples of monomers M5 having a urea group (hereinafter referred to as monomer M5b) are C1-C4-alkyl esters of acrylic acid or methacrylic acid and N-C1-C4-alkylamides of acrylic acid or methacrylic acid, wherein the C1-C4-alkyl group has a urea group or a 2-side-oxyimidazoline group, such as 2-(2-side-oxy-imidazolidin-1-yl)ethyl acrylate and 2-(2-side-oxy-imidazolidin-1-yl)ethyl methacrylate (which are also known as 2-ureidoacrylate and 2-ureidomethacrylate, respectively). N-(2-Acryloyloxyethyl)urea, N-(2-methacryloyloxyethyl)urea, N-(2-(2-side-oxy-imidazolidine-1-yl)ethyl)acrylamide, N-(2-(2-side-oxy-imidazolidine-1-yl)ethyl)methacrylamide, and ureas substituted with allyl or vinyl groups and 2-side-oxyimidazoline compounds substituted with allyl or vinyl groups (e.g., 1-allyl-2-side-oxyimidazoline, N-allylurea, and N-vinylurea).

[0072] Examples of monomers M5 (hereinafter referred to as monomer M5c) having a ketone group are as follows: - C2-C8-side-oxyalkyl esters of acrylic acid or methacrylic acid and N-C2-C8-side-oxyalkyl amides of acrylic acid or methacrylic acid, such as diacetone acrylamide (DAAM) and diacetone methacrylic acid, and - C1-C4-alkyl esters of acrylic acid or methacrylic acid and N-C1-C4-alkyl amides of acrylic acid or methacrylic acid, wherein the C1-C4-alkyl group has a 2-acetylacetoxy group of the formula OC(=O)-CH2-C(=O)-CH3 (also known as acetylacetoxy), such as acetylacetoxyethyl acrylate, acetylacetoxypropyl methacrylate, acetylacetoxybutyl methacrylate and 2-(acetylacetoxy)ethyl methacrylate.

[0073] Suitable monomer M6 comprises a monoalkenyl unsaturated silane functional monomer (monomer M6a), such as a monomer having at least one mono-, di-, and / or tri-C1-C4-alkoxysilane group in addition to an alkene unsaturated double bond, such as vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxyethyltrimethoxysilane, methacryloxyethyltriethoxysilane, and mixtures thereof. The amount of silane functional monomer M6a (if present) generally does not exceed 1 pphm, and is generally in the range of 0.01 pphm to 1 pphm.

[0074] Suitable monomer M6 also includes a monoolefinic unsaturated monomer (monomer M6b) having at least one epoxy group, specifically a glycidyl group, such as glycidyl acrylate, glycidyl methacrylate, 2-glycidyloxyethyl acrylate, and 2-glycidyloxyethyl methacrylate. The amount of monomer M6b (if present) generally does not exceed 2 pphm, and is generally in the range of 0.01 pphm to 2 pphm.

[0075] Monomer M may also include polyene unsaturated monomers (monomer M7), that is, monomers having at least two non-conjugated olefinic unsaturated double bonds. The amount of such monomer M7 is generally no more than 1 pphm.

[0076] Examples of polyene-based unsaturated monomer M7 include: - Diesters of monoene-based unsaturated C3-C6 monocarboxylic acids and saturated aliphatic or cycloaliphatic diols, specifically diesters of acrylic acid or methacrylate, such as ethylene glycol (1,2-ethylene glycol), 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 diacrylates and dimethacrylates; - Monoesters of monoene-based unsaturated C3-C6 monocarboxylic acids and monoene-based unsaturated aliphatic or cycloaliphatic monohydroxy compounds, such as vinyl alcohol. Acrylates and methacrylates of alcohols, ethenols, allyl alcohols (2-propen-1-ol), 2-cyclohexen-1-ol or norbornenol, such as allyl acrylate and allyl methacrylate; and divinyl aromatic compounds, such as 1,3-divinylbenzene and 1,4-divinylbenzene.

[0077] When exposed to sunlight, the polymeric monoolefin unsaturated copolymerizable UV-initiator M8 causes crosslinking of the polymer chains. Monomer M8 has an olefinic unsaturated double bond, specifically an acrylate or methacrylate group, and a portion that decomposes under UV radiation and thereby forms a free radical. These groups are typically benzophenone, acetophenone, benzoin, or carbonate groups attached to a benzene ring. Such compounds are disclosed, for example, in EP 346734, EP 377199, DE 4037079, DE 3844444, EP 1213, and US2015 / 0152297. Examples include (but are not limited to) 4-propenyloxybenzophenone (= 4-benzoylphenyl acrylate), 4-methpropenyloxybenzophenone (= 4-benzoylphenyl 2-methacrylate), 4-(2-propenyloxyethoxy)benzophenone (= 2-(4-benzoylphenoxy)ethyl acrylate), 4-(2-methpropenyloxyethoxy)benzophenone (= 2-methacrylate 2-(4-benzoylphenoxy)ethyl acrylate), O-(2-(meth)propenyloxyethyl)-O-(benzoylphenyl) carbonate and O-(2-(meth)propenyloxyethyl)-O-(acetylated phenyl) carbonate. The amount of these monomers M7 is usually no more than 1 pphm and when present, they are usually present in amounts from 0.01 pphm to 1 pphm, especially from 0.02 pphm to 0.5 pphm.

[0078] Specifically, monomer M includes at least one monomer M4 and at least one monomer M5.

[0079] Specifically, monomer M comprises the following: - 25% to 90% by weight, particularly 30% to 85% by weight, of isobutyl acrylate, specifically having at least 50 mol-% biochar, based on the total amount of monomer M (as monomer M1); - at least one monomer M2, selected from ethyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, 2-propylheptaacrylate, and mixtures thereof (e.g., mixtures of butyl acrylate and 2-ethylhexyl acrylate, or mixtures of butyl acrylate and ethyl acrylate, or mixtures of ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate and mixtures thereof); - Based on the total amount of monomer M, 10% to 45% by weight, particularly 15% to 45% by weight, of at least one monomer M3, selected from tert-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isoborneol acrylate, isoborneol methacrylate, and styrene and mixtures thereof; - Based on the total amount of monomer M, 0.05% to 4% by weight or 0.1% to 4% by weight, particularly 0.05% to 3.5% by weight or 0.1% to 3.5% by weight or 0.1% to 3% by weight or 0.2% to 3% by weight or 0.5% to 3% by weight or 0.5% to 2% by weight, of one or more monoolefinic unsaturated monomers M4; Based on the total weight of monomer M, 0% to 9.95% by weight, especially 0.1% to 7% by weight or 0.1% to 5% by weight of one or more nonionic monomers M5; - 0% to 1% by weight, especially 0% to 0.5% by weight of one or more monomers M7; The total amount of monomers M1 and M2 based on the olefinic unsaturated monomer M is in the range of 50 wt% to 89.95 wt%, or 50 wt% to 89.85 wt%, or 50 wt% to 89.8 wt%, or 50 wt% to 89.7 wt%, or 50 wt% to 89.4 wt%, particularly 55 wt% to 84.95 wt%, or 55 wt% to 84.85 wt%, or 55 wt% to 84.8 wt%, or 55 wt% to 84.7 wt%, or 55 wt% to 84.4 wt%, and the total amount of monomers M1, M2 and M3 based on the olefinic unsaturated monomer M is at least 90 wt%, specifically at least 94.4 wt%, or at least 94.7 wt%, or at least 94.8 wt%, or at least 94.9 wt% (Example Group 4).

[0080] More specifically, monomer M includes: - 25% to 90% by weight, particularly 30% to 85% by weight, of isobutyl acrylate, specifically having at least 50 mol-% biochar, based on the total amount of monomer M (as monomer M1); - at least one monomer M2, selected from n-butyl acrylate and 2-ethylhexyl acrylate, and mixtures thereof, based on the total amount of monomer M; - at least one monomer M3, selected from tributyl acrylate, n-butyl methacrylate, methyl methacrylate, cyclohexyl methacrylate, isocamphenyl methacrylate, and styrene, and mixtures thereof, based on the total amount of monomer M; Based on the total amount of monomer M, 0.05 wt% to 4 wt% or 0.1 wt% to 4 wt%, especially 0.05 wt% to 3.5 wt%, or 0.1 wt% to 3.5 wt%, or 0.1 wt% to 3 wt%, or 0.2 wt% to 3 wt%, or 0.5 wt% to 3 wt%, or 0.5 wt% to 2 wt% of one or more monoolefinic unsaturated monomers M4; - Based on the total weight of monomer M, 0 wt% to 9.95 wt%, especially 0.1 wt% to 7 wt%, or 0.1 wt% to 5 wt% of one or more nonionic monomers M5; - 0 wt% to 1 wt%, especially 0 wt% to 0.5 wt% of one or more monomers M7; The total amount of monomers M1 and M2 based on the olefinic unsaturated monomer M is in the range of 50 wt% to 89.95 wt%, or 50 wt% to 89.85 wt%, or 50 wt% to 89.8 wt%, or 50 wt% to 89.7 wt%, or 50 wt% to 89.4 wt%, particularly 55 wt% to 84.95 wt%, or 55 wt% to 84.85 wt%, or 55 wt% to 84.8 wt%, or 55 wt% to 84.7 wt%, or 55 wt% to 84.4 wt%, and wherein the total amount of monomers M1, M2 and M3 based on the olefinic unsaturated monomer M is at least 90 wt%, specifically at least 94.4 wt%, or at least 94.7 wt%, or at least 94.8 wt%, or at least 94.9 wt% (Example Group 4a).

[0081] Even more preferably, monomer M comprises: - 25% to 90% by weight, particularly 30% to 85% by weight, of isobutyl acrylate, specifically having at least 50 mol-% biochar, based on the total amount of monomer M (as monomer M1); - 0% to 50% by weight, for example 5% to 50% by weight, particularly 0% to 40% by weight or 5% to 40% by weight, of at least one monomer M2, selected from n-butyl acrylate and 2-ethylhexyl acrylate and mixtures of n-butyl acrylate and 2-ethylhexyl acrylate, based on the total amount of monomer M; - 10% to 45% by weight, particularly 15% to 45% by weight, of monomer M3, selected from methyl methacrylate and combinations of methyl methacrylate and at least one other monomer M3 selected from tributyl acrylate, n-butyl methacrylate, cyclohexyl methacrylate, isocamphenyl methacrylate and styrene; - Based on the total amount of monomer M, 0.05 wt% to 4 wt% or 0.1 wt% to 4 wt%, especially 0.05 wt% to 3.5 wt%, or 0.1 wt% to 3.5 wt%, or 0.1 wt% to 3 wt%, or 0.2 wt% to 3 wt%, or 0.5 wt% to 3 wt%, or 0.5 wt% to 2 wt% of one or more monoolefinic unsaturated monomers M4; - Based on the total weight of monomer M, 0 wt% to 9.95 wt%, especially 0.1 wt% to 7 wt%, or 0.1 wt% to 5 wt% of one or more nonionic monomers M5; - 0 wt% to 1 wt%, especially 0 wt% to 0.5 wt% of one or more monomers M7; The total amount of monomers M1 and M2 based on the olefinic unsaturated monomer M is in the range of 50 wt% to 89.95 wt%, or 50 wt% to 89.85 wt%, or 50 wt% to 89.8 wt%, or 50 wt% to 89.7 wt%, or 50 wt% to 89.4 wt%, particularly 55 wt% to 84.95 wt%, or 55 wt% to 84.85 wt%, or 55 wt% to 84.8 wt%, or 55 wt% to 84.7 wt%, or 55 wt% to 84.4 wt%, and the total amount of monomers M1, M2 and M3 based on the olefinic unsaturated monomer M is at least 90 wt%, specifically at least 94.4 wt%, or at least 94.7 wt%, or at least 94.8 wt%, or at least 94.9 wt% (Example Group 4b).

[0082] In particular, monomer M comprises: - 25% to 90% by weight, especially 30% to 85% by weight, of isobutyl acrylate, specifically having at least 50 mol-% biochar, based on the total amount of monomer M (as monomer M1); - at least one monomer M2, selected from n-butyl acrylate and 2-ethylhexyl acrylate, and mixtures of n-butyl acrylate and 2-ethylhexyl acrylate, based on the total amount of monomer M; - 10% to 45% by weight, especially 15% to 45% by weight, of methyl methacrylate (as monomer M3), based on the total amount of monomer M; Based on the total amount of monomer M, 0.05 wt% to 4 wt% or 0.1 wt% to 4 wt%, especially 0.05 wt% to 3.5 wt%, or 0.1 wt% to 3.5 wt%, or 0.1 wt% to 3 wt%, or 0.2 wt% to 3 wt%, or 0.5 wt% to 3 wt%, or 0.5 wt% to 2 wt% of one or more monoolefinic unsaturated monomers M4; - Based on the total weight of monomer M, 0 wt% to 9.95 wt%, especially 0.1 wt% to 7 wt%, or 0.1 wt% to 5 wt% of one or more nonionic monomers M5; - 0 wt% to 1 wt%, especially 0 wt% to 0.5 wt% of one or more monomers M7; The total amount of monomers M1 and M2, based on the total amount of olefinic unsaturated monomer M, is in the range of 50 wt% to 89.95 wt%, or 50 wt% to 89.85 wt%, or 50 wt% to 89.8 wt%, or 50 wt% to 89.7 wt%, or 50 wt% to 89.4 wt%, particularly 55 wt% to 84.95 wt%, or 55 wt% to 84.85 wt%, or 55 wt% to 84.8 wt%, or 55 wt% to 84.7 wt%, or 55 wt% to 84.4 wt%, and the total amount of monomers M1, M2 and M3, based on the total amount of olefinic unsaturated monomer M, is at least 90 wt%, specifically at least 94.4 wt%, or at least 94.7 wt%, or at least 94.8 wt%, or at least 94.9 wt% (Example Group 4c).

[0083] In the specific embodiment group 5, the types and amounts of monomers M1, M2, M3 and M4 are as defined in the specific embodiment group 4, except that monomer M1 is isoamyl acrylate instead of isobutyl acrylate.

[0084] In the Specific Embodiment Group 5, the preferred embodiment is Embodiment 5a, wherein the type and amount of monomers M1, M2, M3, M4 and M5 are as defined in the Specific Embodiment Group 4a, except that monomer M1 is isoamyl acrylate instead of isobutyl acrylate.

[0085] In particular, in the group 5 of specific embodiments, the preferred embodiment is 5b, wherein the type and amount of monomers M1, M2, M3, M4 and M5 are as defined in the group 4b of more preferred embodiments, except that monomer M1 is isoamyl acrylate instead of isobutyl acrylate.

[0086] In the Specific Embodiment Group 5, the preferred embodiment is Embodiment 5c, wherein the type and amount of monomers M1, M2, M3, M4 and M5 are as defined in the Specific Embodiment Group 4c, except that monomer M1 is isoamyl acrylate instead of isobutyl acrylate.

[0087] In the Specific Embodiment Group 6, the types and amounts of monomers M1, M2, M3, M4 and M5 are as defined in the Specific Embodiment Group 4, except that monomer M1 is a mixture of at least 80% by weight (based on the total amount of monomer M1) isoamyl acrylate and 2-methyl butyl acrylate and, where appropriate, up to 20% isobutyl acrylate, instead of isobutyl acrylate.

[0088] In the Specific Embodiment Group 6, the preferred embodiment is Embodiment 6a, wherein the types and amounts of monomers M1, M2, M3, M4 and M5 are as defined in the Specific Embodiment Group 4a, except that monomer M1 is a mixture of at least 80% by weight (based on the total amount of monomer M1) of isoamyl acrylate and 2-methyl butyl acrylate and, where appropriate, up to 20% of isobutyl acrylate, instead of isobutyl acrylate.

[0089] In particular, in the group 6 of specific embodiments, the preferred embodiment is 6b, wherein the types and amounts of monomers M1, M2, M3, M4 and M5 are as defined in the group 4b of more preferred embodiments, except that monomer M1 is a mixture of at least 80% by weight (based on the total amount of monomer M1) of isoamyl acrylate and 2-methyl butyl acrylate and, where appropriate, up to 20% of isobutyl acrylate, instead of isobutyl acrylate.

[0090] In the Specific Embodiment Group 6, the preferred embodiment is Embodiment 6c, wherein the types and amounts of monomers M1, M2, M3, M4 and M5 are as defined in the Specific Embodiment Group 4c, except that monomer M1 is a mixture of at least 80% by weight (based on the total amount of monomer M1) of isoamyl acrylate and 2-methyl butyl acrylate and, where appropriate, up to 20% of isobutyl acrylate, instead of isobutyl acrylate.

[0091] Another embodiment, group 7, relates to the polymer latex of the present invention, wherein monomer M comprises or consists of the following: a) 50% to 70% by weight of isobutyl acrylate (as monomer M1) based on the total weight of monomer M; b) 30% to 50% by weight of methyl methacrylate (as monomer M3) based on the total weight of monomer M; c) 0.1% to 4% by weight, particularly 0.2% to 3% by weight or 0.5% to 3% by weight, especially 0.5% to 2% by weight of one or more monomers M4, selected from the group consisting of monoolefin unsaturated carboxylic acids; d) 0% to 5% by weight, particularly 0.1% to 4% by weight, preferably 0.2% to 3% by weight or 0.5% to 3% by weight, even more preferably 1% to 3% by weight of one or more monoolefin unsaturated carboxylic acids amide (as monomer M5) based on the total weight of monomer M; e) From 0% to 10% by weight, one or more other olefinic unsaturated nonionic monomers different from monomers M1, methyl methacrylate, M4, and M5, preferably selected from monomers M2 and M3 different from methyl methacrylate, for example, from the group consisting of: tert-butyl acrylate, n-butyl acrylate, n-pentyl acrylate, C6-C10 alkyl acrylates (specifically 2-propylheptyl acrylate, n-octyl acrylate, 2-octyl acrylate, 2-ethylhexyl acrylate), C2-C10 alkyl methacrylates (specifically 2-ethylhexyl methacrylate, butyl methacrylate, and tert-butyl methacrylate), and vinyl aromatic monomers (specifically styrene).

[0092] In Example Group 7, isobutyl acrylate (IBA) and methyl methacrylate (MMA) comprise at least 95% by weight of monomer composition M. For example, isobutyl acrylate may be present in an amount of 55% to 65% by weight of monomer M, and methyl methacrylate may be present in an amount of 35% to 45% by weight of monomer M.

[0093] In the preferred subgroup 7a of Example Group 7, the monomer composition M consists of the following: a) 50% to 69.8% by weight, particularly 55% to 64.8% by weight of isobutyl acrylate, b) 30% to 49.8% by weight, particularly 35% to 44.8% by weight of methyl methacrylate, c) 0.1% to 4% by weight, specifically 0.2% to 3% by weight or 0.5% to 3% by weight, particularly 0.5% to 2% by weight of monoalkenyl unsaturated carboxylic acid, d) 0.1% to 4% by weight, preferably 0.2% to 3% by weight or 0.5% to 3% by weight, even more preferably 1% to 3% by weight of monoalkenyl unsaturated carboxylic acid amide, wherein the weight percentage values ​​are relative to the total weight of monomer M.

[0094] In the best subgroup 7b of Example Group 7, the monomer composition M consists of the following: a) 50% to 69.6% by weight, particularly 55% to 64.6% by weight or 55% to 64% by weight of isobutyl acrylate, b) 30% to 49.6% by weight, particularly 35% to 44.6% by weight or 35% to 44% by weight of methyl methacrylate, c) 0.2% to 3% by weight, particularly 0.5% to 3% by weight, particularly 0.5% to 2% by weight of monoalkenyl unsaturated carboxylic acids selected from acrylic acid, methacrylic acid and itaconic acid, d) 0.2% to 3% by weight, particularly 0.5% to 3% by weight, particularly 0.5% to 2% by weight of monoalkenyl unsaturated carboxylic acids selected from acrylamide and methacrylamide, wherein the weight percentage values ​​are relative to the total weight of monomer M.

[0095] For example, in Example Subgroup 7b, the monomer composition M consists of the following: a) 50% to 69% by weight, especially 55% to 64% by weight of isobutyl acrylate, b) 30% to 49% by weight, especially 35% to 44% by weight of methyl methacrylate, c) 0.5% to 3% by weight, especially 0.5% to 2% by weight of acrylic acid, d) 0.5% to 3% by weight, especially 0.5% to 2% by weight of acrylamide, wherein the weight percentages are relative to the total weight of monomer M.

[0096] For example, in the subgroup 7b of the examples, the monomer composition M consists of the following: a) 50% to 69% by weight, especially 55% to 64% by weight of isobutyl acrylate, b) 30% to 49% by weight, especially 35% to 44% by weight of methyl methacrylate, c) 0.5% to 3% by weight, especially 0.5% to 2% by weight of methacrylic acid, d) 0.5% to 3% by weight, especially 0.5% to 2% by weight of acrylamide.

[0097] In a preferred embodiment of Example Group 7, at least a portion of the isobutyl acrylate of component a) is derived from renewable raw materials, that is, at least a portion of the isobutyl acrylate of component a) is a bio-based isobutyl acrylate obtained partially or entirely from renewable raw materials. A mixture of isobutyl acrylate obtained from fossil raw materials and isobutyl acrylate obtained partially or entirely from renewable raw materials may also be used.

[0098] Preferably, the copolymer particles contained in the polymer latex have a Z-mean particle size in the range of 30 nm to 500 nm, and specifically in the range of 40 nm to 450 nm, as determined by QELS. The particle size distribution of the copolymer particles contained in the polymer latex may be unimodal or near-unimodal, meaning that the particle size distribution function has a single maximum value and no specific shoulder. The particle size distribution of the copolymer particles contained in the polymer latex may also be multimodal or near-multimodal, meaning that the particle size distribution function has at least two different maximum values ​​or at least one maximum value and at least one obvious shoulder.

[0099] Unless otherwise stated, particle size and particle size distribution are determined by quasi-elastic light scattering (QELS) (also known as dynamic light scattering (DLS)). The measurement method is described in ISO 13321:1996. The measurement can be performed using a high-performance particle size analyzer (HPPS). For this purpose, a sample of the aqueous polymer latex is diluted and the diluent is analyzed. In the context of QELS, depending on the particle size, the aqueous diluent may have a polymer concentration ranging from 0.001 wt% to 0.5 wt%. For most purposes, a suitable concentration is 0.01 wt%. However, higher or lower concentrations can be used to achieve the optimal signal / noise ratio. Dilution can be achieved by adding the polymer latex to water or an aqueous surfactant solution (to avoid flocculation). Typically, dilution is performed using an aqueous solution of 0.1 wt% of a nonionic emulsifier (e.g., ethoxylated C16 / C18 alkanols (degree of ethoxylation 18)) as the diluent. Measurement configuration: HPPS from Malvern, automated, using continuous flow cuvettes and a Gilson autosampler. Parameters: Measurement temperature: 20.0℃; Measurement time: 120 seconds (6 cycles per 20 s); Scattering angle: 173°; Laser wavelength: 633 nm (HeNe); Medium refractive index: 1.332 (aqueous solution); Viscosity: 0.9546 mPa·s. This measurement provides the average value (fitted average value) of the second-order cumulant analysis, i.e., the Z-mean. The "fitted average value" is the average, intensity-weighted hydrodynamic particle size (expressed in nm).

[0100] Hydrodynamic particle size can also be determined by hydrodynamic chromatography-division (HDC), as illustrated, for example, in H. Wiese, "Characterization of Aqueous Polymer Dispersions", Polymer Dispersions and Their Industrial Applications (Wiley-VCH, 2002), pp. 41-73. For further details, see the examples and descriptions below.

[0101] In certain group of embodiments, the copolymer particles contained in the polymer latex have a Z-mean particle size in the range of 30 nm to 200 nm, and specifically in the range of 40 nm to 150 nm, as determined by QELS. In these particular group of embodiments, the particle size distribution of the copolymer particles contained in the polymer latex is specifically unimodal or near-unimodal, meaning that the particle size distribution function has a single maximum value.

[0102] In another specific group of embodiments, the copolymer particles contained in the polymer latex have a Z-mean particle size in the range of 150 nm to 500 nm, and specifically in the range of 200 nm to 400 nm, as determined by QELS. In this specific group of embodiments, the particle size distribution of the copolymer particles contained in the polymer latex is specifically multimodal and specifically bimodal, meaning that the particle size distribution function has at least two maximum values. Typically, the particle size distribution of polymer particles in a polymer dispersion obtained by the process described herein (as determined by QELS) has a first maximum value in the range of 30 nm to 150 nm and a second maximum value in the range of 200 nm to 500 nm. Preferably, the first maximum value is in the range of 50 nm to 130 nm and the second maximum value is in the range of 200 nm to 400 nm.

[0103] The copolymer contained in the polymer particles may form a single phase, or may form different phases when the polymer particles contain copolymers that differ in monomer composition. Preferably, the polymer particles contained in the aqueous polymer latex of the present invention comprise at least one polymer phase, wherein the polymer has a glass transition temperature Tg of no more than 40°C, specifically at most 25°C (e.g., in the range of -25°C to +40°C, specifically in the range of -20°C to +25°C).

[0104] The glass transition temperature mentioned herein is the actual glass transition temperature. The actual glass transition temperature can be determined experimentally by differential scanning calorimetry (DSC) according to ISO 11357-2:2013, preferably using a sample prepared according to ISO 16805:2003.

[0105] According to the present invention embodiment of the Yujia Group, the polymer particles contained in the aqueous polymer latex of the present invention include a polymer phase (1) (having a glass transition temperature Tg (1) in the range of -25°C to +40°C, specifically in the range of -20°C to +20°C) and a polymer phase (2) (having a glass transition temperature Tg (2) in the range of +50°C to +150°C, specifically in the range of +60°C to +120°C).

[0106] Preferably, based on the total amount of monomer M1 present in monomer M, at least 75% by weight of monomer M1 is present in polymer phase (1).

[0107] The actual glass transition temperature depends on the monomer composition that forms the respective polymer phases (1) and (2), and the theoretical glass transition temperature can be calculated from the monomer composition used in emulsion polymerization. The theoretical glass transition temperature is usually calculated from the monomer composition using the Fox equation: 1 / Tgt = xa / Tga + xb / Tgb + ... xn / Tgn, where xa, xb, ... xn are the mass fractions of monomers a, b, ... n, and Tga, Tgb, ... Tgn are the actual glass transition temperatures (expressed as Kelvin temperatures) of homopolymers synthesized in a single step from only one of monomers 1, 2, ... n. The Fox equation is presented in TG Fox, Bull. Am. Phys. Soc. 1956, 1, p. 123 and in Ullmann's Encyclopädie der technischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], Vol. 19, p. 18, 4th edition, Verlag Chemie, Weinheim, 1980. The actual Tg values ​​of most monomer homopolymers are known and listed (for example) in Ullmann's Encyclopädie der technischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], 5th edition, Vol. A21, p. 169, Verlag Chemie, Weinheim, 1992. Other sources of glass transition temperature for homopolymers include (e.g.) J. Brandrup, EH Immergut, Polymer Handbook, 1st edition, J. Wiley, New York 1966; 2nd edition, J. Wiley, New York 1975; 3rd edition, J. Wiley, New York 1989; and 4th edition, J. Wiley, New York 2004.

[0108] Generally, the theoretical glass transition temperature Tgt calculated according to the Fox equation as described herein and the glass transition temperature measured experimentally as described herein are similar or even the same, and do not deviate from each other by more than 5 K, specifically by no more than 2 K. Therefore, the actual glass transition temperature and theoretical glass transition temperature of polymer phases (1) and (2) can be adjusted by selecting appropriate monomers Ma, Mb...Mn and their mass fractions xa, xb,...xn in the monomer composition to achieve the desired glass transition temperatures Tg(1) and Tg(2), respectively. Those skilled in this art should know how to select appropriate amounts of monomers Ma, Mb...Mn to obtain copolymers and / or copolymer phases with the desired glass transition temperatures.

[0109] Preferably, the monomer composition forming the polymer phase (1) is selected such that the theoretical glass transition temperature Tgt (1) is preferably in the range of -25°C to +40°C, and especially in the range of -20°C to 20°C. Similarly, the monomer composition forming the polymer phase (2) is selected such that the theoretical glass transition temperature Tgt (2) is preferably in the range of +50°C to +150°C, and more preferably in the range of 60°C to 120°C.

[0110] Specifically, the relative amounts of the monomers forming the polymer phase (1) and the monomers forming the polymer phase (2) are selected such that the monomer M includes - based on the total amount of monomer M, 50 wt.-% to 95 wt.-%, preferably 60 wt.-% to 90 wt.-%, of the monomers forming the polymer phase (1) having a lower glass transition temperature Tg (1) and - based on the total amount of monomer M, 5 wt.-% to 50 wt.-%, preferably 10 wt.-% to 40 wt.-%, of the monomers forming the polymer phase (2) having a higher glass transition temperature Tg (2).

[0111] Therefore, the polymer particles contained in the polymer dispersion that can be obtained by the process of the present invention include - 50 wt.-% to 95 wt.-%, preferably 60 wt.-% to 90 wt.-% of a polymer phase (1) having a lower glass transition temperature Tg (1) based on the total weight of the polymer particles and - 5 wt.-% to 50 wt.-%, preferably 10 wt.-% to 40 wt.-% of a polymer phase (2) having a higher glass transition temperature Tg (2) based on the total weight of the polymer particles.

[0112] Those skilled in the art will understand that the monomer M forming the polymer phase (1) and the monomer M forming the polymer phase (2) may differ in terms of monomer type and / or relative amount. It is evident that the monomer M forming the polymer phase (2) contains a higher amount of monomers that produce a high glass transition temperature. In one group of embodiments, the relative amount of monomer M3 in the monomer M forming the polymer phase (2) is higher than that in the monomer M forming the polymer phase (1). In another group of embodiments, the relative amount of monomer M3 in the monomer M forming the polymer phase (1) is higher than that in the monomer M forming the polymer phase (2). However, the overall composition of the monomer M forming the polymer phase (1) and the monomer M forming the polymer phase (2) is within the aforementioned range.

[0113] Preferably, the aqueous polymer dispersion of the present invention has a pH of at least 6, for example, in the pH range of 6 to 9.

[0114] The aqueous polymer dispersion of the present invention typically has a solids content ranging from 30% to 75% by weight, preferably from 40% to 65% by weight, and specifically from 45% to 60% by weight. Solids content describes the proportion of non-volatile components. The solids content of the dispersion is determined using infrared moisture analysis with a balance. In this determination, a certain amount of polymer dispersion is introduced into the instrument, heated to 140°C, and then maintained at that temperature. Once the average weight decreases to below 1 mg within 140 seconds, the measurement procedure is immediately terminated. The ratio of the dried weight to the original introduced mass gives the solids content of the polymer dispersion. The total solids content of the formulation is determined arithmetically from the amount of added substance and its solids content and concentration.

[0115] The polymer dispersion may contain a crosslinking agent for post-crosslinking polymer latex particles, provided that the polymer in the polymer latex has functional groups complementary to the functional groups of the crosslinking agent. In this context, the term "complementary" should be understood as a chemical reaction in which the functional groups of the latex and the functional groups of the crosslinking agent readily form chemical bonds between the atoms of the respective functional groups. Typically, the crosslinking agent has at least two functional groups complementary to the functional groups of the polymer in the polymer latex. Examples of suitable crosslinking agents are described below.

[0116] In addition to the polymer and optional crosslinking agent, the aqueous polymer dispersion of the present invention may also contain other components commonly found in aqueous polymer dispersions. These other components are, for example, surfactants, such as emulsifiers and protective colloids, specifically used to generate polymer latex, other defoamers, and the like. Other components may also be acids, bases, buffers, polymerization reaction decomposition products, deodorizing compounds, and chain transfer agents. Furthermore, the polymer latex may contain biocides to prevent microbial damage. Based on the total weight of the polymer dispersion, the amount of each component typically does not exceed 1.5 wt%. Based on the total weight of the polymer latex, the total amount of these stated components typically does not exceed 5 wt%.

[0117] Preferably, based on the total weight of the polymer latex, the amount of volatile organic matter, that is, the content of organic compounds with a maximum boiling point of 250°C under standard conditions (101,325 kPa) (as determined by gas chromatography according to ISO 17895:2005), is less than 0.5% by weight, and specifically less than 0.2% by weight.

[0118] In addition to the polymer, the aqueous polymer latex also contains an aqueous phase in which polymer particles of the polymer latex are dispersed. The aqueous phase (also known as the slurry) is essentially composed of water and any other water-insoluble components. Based on the total weight of the aqueous phase, the total concentration of any other components is generally no more than 10 wt%, specifically 8 wt%.

[0119] The aqueous polymer latex of the present invention can be prepared by any method of preparing an aqueous dispersion of the polymer obtained from the polymer monomer M. Specifically, the aqueous polymer latex of the present invention is prepared by aqueous emulsion polymerization of monomer M, and specifically by free radical aqueous emulsion polymerization. The term "free radical aqueous emulsion polymerization" means that the polymerization of monomer M is initiated by free radicals formed by the decay of a polymerization initiator, wherein the free radicals are formed in the polymerization mixture. It is also referred to as "free radical-initiated emulsion polymerization". The procedures for free radical-initiated emulsion polymerization of monomers in aqueous media have been extensively described and are well-known to those familiar with this technique. [For reference, see Emulsion Polymerization in Encyclopedia of Polymer Science and Engineering, Vol. 8, pp. 659 and up (1987); DC Blackley, High Polymer Latices, Vol. 1, pp. 35 and up (1966); H. Warson, The Applications of Synthetic Resin Emulsions, Chapter 5, pp. 246 and up (1972); D. Diederich, Chemie in unserer Zeit 24, pp. 135-142 (1990); Emulsion Polymerisation, Interscience Publishers, New York (1965); DE-A 40 03 422; and Dispersionen synthetischer Hochpolymerer, F. Hölscher, Springer-Verlag, Berlin.] (1969)]. The typical procedure for aqueous emulsion polymerization of olefinic unsaturated monomers is also described in the patent documents discussed in the preamble of this patent application.

[0120] Free radical-initiated aqueous emulsion polymerization is typically carried out by emulsifying an olefinic unsaturated monomer in an aqueous medium to form an aqueous phase, usually achieved by using a surfactant compound (e.g., an emulsifier and / or a protective colloid); and by using at least one initiator to polymerize the system, the initiator decaying by forming free radicals and thereby initiating chain growth addition polymerization of the olefinic unsaturated monomer M. The difference between the preparation of aqueous polymer dispersions according to the present invention and this general procedure may be only in the specific use of the monomers M1 to M8 mentioned above. It should be understood here that, for the purposes of this specification, the process should also cover seed, staged, one-off, and gradient methods well known to those skilled in the art.

[0121] Free radical-initiated aqueous emulsion polymerization is triggered by a free radical polymerization initiator (free radical initiator). In principle, such initiators can be peroxides or azo compounds. Of course, redox initiator systems can also be used. In principle, the peroxides used can be inorganic peroxides, such as hydrogen peroxide or peroxydisulfate, such as mono- or dialkali metal or ammonium salts of peroxydisulfate, such as mono- and disodium, potassium or ammonium salts; or organic peroxides, such as alkyl hydroperoxides (e.g., tert-butyl hydroperoxide, p-menthyl hydroperoxide or isopropylphenyl hydroperoxide) and dialkyl or diaryl peroxides (e.g., di-tert-butyl or diisopropylphenyl peroxide). The azo compounds used are mainly 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), and 2,2'-azobis(amidinylpropyl) dihydrochloride (AIBA, corresponding to V-50 from Wako Chemicals). Suitable oxidants for redox initiator systems are primarily the peroxides specified above. Corresponding reducing agents that can be used are sulfur compounds with low oxidation states (e.g., alkali metal sulfites (e.g., potassium sulfite and / or sodium sulfite), alkali metal bisulfites (e.g., potassium bisulfite and / or sodium bisulfite), alkali metal metabisulfites (e.g., potassium metabisulfite and / or sodium metabisulfite), hydroxymethyl sulfinates (e.g., potassium hydroxymethyl sulfinate and / or sodium hydroxymethyl sulfinate), alkali metal salts (specifically, potassium and / or sodium salts of aliphatic sulfinic acids) and alkali metal hydrosulfides (e.g., potassium and / or sodium hydrosulfides)), polyvalent metal salts (e.g., ferric(II) sulfate, ferric(II) ammonium sulfate, ferric(II) phosphate), olefins (e.g., dihydroxymaleic acid, benzoin and / or ascorbic acid), and reducing sugars (e.g., sorbitol, glucose, fructose and / or dihydroxyacetone).

[0122] Preferred free radical initiators are inorganic peroxides, especially peroxydisulfate.

[0123] Generally speaking, based on the total amount of monomer M, the amount of free radical initiator used is 0.05 pphm to 2 pphm, preferably 0.1 pphm to 1 pphm.

[0124] The amount of free radical initiator required for the emulsion polymerization of monomer M can be completely loaded into the polymerization vessel initially. However, it is also possible to either not load or load only a portion of the free radical initiator (e.g., based on the total amount of free radical initiator not exceeding 30% by weight, especially not exceeding 20% ​​by weight), and then add any remaining amount of free radical initiator to the free radical polymerization reaction under polymerization conditions. Preferably, under polymerization conditions, at least 70%, specifically at least 80%, especially at least 90%, or all of the polymerization initiator is supplied to the free radical polymerization reaction. During the free radical emulsion polymerization of monomer M, monomer M can be continuously supplied in one or more batches or at a constant or varying flow rate, depending on consumption.

[0125] Generally, the term "polymerization conditions" should be understood to refer to the temperature and pressure at which free radical-initiated aqueous emulsion polymerization proceeds at a sufficient polymerization rate. This depends particularly on the free radical initiator used. It is advantageous to select the type and amount of free radical initiator, the polymerization temperature, and the polymerization pressure so that there is always a sufficient amount of initiating free radicals to initiate or sustain the polymerization reaction.

[0126] Preferably, the free radical emulsion polymerization of monomer M is carried out by a so-called feed process (also known as a monomer feed method), which means that during the metering period P, at least 80%, specifically at least 90%, or all of the monomer M to be polymerized is metered into the polymerization reaction under polymerization conditions. It can be added part-wise and preferably continuously using a constant or varying feed rate. The duration of period P can depend on the production equipment and can be, for example, from 20 minutes to 12 hours. Typically, the duration of period P is in the range of 0.5 hours to 8 hours, particularly 1 hour to 6 hours. In multi-step emulsion polymerization steps, the total duration of all steps is usually within the above range. The duration of individual steps is usually shorter. Preferably, at least 70%, specifically at least 80%, particularly at least 90%, or all of the polymerization initiator is introduced into the emulsion polymerization simultaneously with the addition of the monomer.

[0127] Aqueous free radical emulsion polymerization is typically carried out in the presence of one or more suitable surfactants. These surfactants typically include emulsifiers and provide microcells, which are the sites of polymerization and serve to stabilize monomer droplets during aqueous emulsion polymerization and during the growth of polymer particles. The surfactants used in emulsion polymerization are typically not separated from the polymer dispersion but are retained in the aqueous polymer dispersion obtainable by emulsion polymerization of monomer M.

[0128] Surfactants can be selected from emulsifiers and protective colloids. Unlike emulsifiers, protective colloids should be understood as polymeric compounds with a molecular weight higher than 2000 Daltons, while emulsifiers typically have a lower molecular weight. Surfactants can be anionic surfactants, nonionic surfactants, or mixtures of nonionic and anionic surfactants.

[0129] Anionic surfactants typically have at least one anionic group, usually selected from phosphoric acid, phosphonic acid, sulfuric acid, and sulfonic acid groups. Anionic surfactants having at least one anionic group are typically used in the form of their alkali metal salt, especially their sodium salt or their ammonium salt.

[0130] The preferred anionic surfactant is an anionic emulsifier, specifically having at least one sulfate group or sulfonic acid group. Similarly, an anionic emulsifier having at least one phosphate group or phosphonate group can be used, either as the sole anionic emulsifier or in combination with one or more anionic emulsifiers having at least one sulfate group or sulfonic acid group.

[0131] Examples of anionic emulsifiers having at least one sulfate or sulfonic acid group include (for example): - alkyl sulfate esters, especially salts of C8-C22-alkyl sulfate esters, especially alkali metal salts and ammonium salts; - ethoxylated alkanol sulfate monoesters, especially salts of ethoxylated C8-C22-alkanols (preferably having an ethoxylation degree (EO degree) in the range of 2 to 40), especially alkali metal salts and ammonium salts; - alkyl sulfonic acids, especially salts of C8-C22-alkyl sulfonic acids, especially alkali metal salts and ammonium salts; - dialkyl esters, especially salts of di-C4-C18-alkyl esters of sulfosuccinic acids, especially alkali metal salts and ammonium salts; - alkylbenzene sulfonic acids, especially salts of C4-C22-alkylbenzene sulfonic acids, especially alkali metal salts and ammonium salts; and - Salts of mono- or disulfonated, alkyl-substituted diphenyl ethers, such as bis(phenylsulfonic acid) ethers having C4-C24-alkyl groups on one or both aromatic rings, especially alkali metal salts and ammonium salts. The latter are common knowledge (e.g., from US-A-4,269,749) and commercially available (e.g., in the form of Dowfax® 2A1 (Dow Chemical Company)), - surfactants having polymerizable olefinic unsaturated double bonds as described herein, such as compounds of formulas (I)-(IV), wherein X and Y are SO3- or O-SO3-, respectively.

[0132] Examples of anionic emulsifiers having a phosphate group or a phosphonate group include (but are not limited to) the following salts selected from the following groups: - mono- and dialkyl phosphates, especially salts of C8-C22-alkyl phosphates, especially alkali metal salts and ammonium salts, - Salts, especially alkali metal salts and ammonium salts, of phosphate monoesters of C2-C3-alkoxylated alkanols (preferably having an alkoxylation degree in the range of 2 to 40, particularly in the range of 3 to 30), such phosphate monoesters being, for example, phosphate monoesters of ethoxylated C8-C22-alkanols (preferably having an ethoxylation degree (EO degree) in the range of 2 to 40), phosphate monoesters of propoxylated C8-C22-alkanols (preferably having a propoxylation degree (PO degree) in the range of 2 to 40), and phosphate monoesters of ethoxylated-co-propoxylated C8-C22-alkanols (preferably having an ethoxylation degree (EO degree) in the range of 1 to 20 and a propoxylation degree of 1 to 20), - alkylphosphonic acids, especially salts of C8-C22-alkylphosphonic acids, especially alkali metal salts and ammonium salts; and - Alkylphenylphosphonic acids, especially salts of C4-C22-alkylphenylphosphonic acids, especially alkali metal salts and ammonium salts. - Surfactants having polymerizable olefinic unsaturated double bonds as described herein, such as compounds of formulas (I)-(IV), wherein X and Y are HPO3-, PO32-, O-HPO3- or O-PO32-, respectively.

[0133] Anionic emulsifiers may also include emulsifiers having polymerizable double bonds, such as emulsifiers of formulas (I) to (IV) and their salts, specifically their alkali metal salts or ammonium salts: In formula (I), R1 is H, C1-C20-alkyl, C5-C10-cycloalkyl, or, where applicable, a phenyl substituted with C1-C20-alkyl, R2 and R2' are both H or together O, R3 and R4 are H or methyl, m is 0 or 1, n is an integer from 1 to 100 and X is SO3-, O-SO3-, O-HPO3- or O-PO32-. (II) In formula (II), R is H, C1-C20-alkyl, C5-C10-cycloalkyl, or, where applicable, a phenyl substituted with C1-C20-alkyl, k is 0 or 1 and X is SO3-, O-SO3-, O-HPO3- or O-PO32-. (III) In formula (III), R1 refers to H, C1-C20-alkyl, O-C1-C20-alkyl, C5-C10-cycloalkyl, O-C5-C10-cycloalkyl, or O-phenyl substituted with C1-C20-alkyl as appropriate, n refers to an integer from 1 to 100, and Y refers to SO3-, HPO3-, or PO32-. (IV) In formula (IV), R1 refers to H, C1-C20-alkyl, or 1-phenylethyl, R2 refers to H, C1-C20-alkyl, or 1-phenylethyl, A refers to C2-C4-alkyldiyl (e.g., 1,2-ethylenediyl, 1,2-propanediyl, 1,2-butadiyl, or 1,4-butadiyl), n refers to an integer from 1 to 100, and Y refers to SO3-, HPO3-, or PO32-.

[0134] Specific embodiments of the copolymerizable emulsifier of formula (I) are referred to as sulfate or phosphate esters of polyethylene glycol monoacrylate. Specific embodiments of the copolymerizable emulsifier of formula (I) may also be referred to as phosphonate or allyl ether sulfate of polyethylene glycol monoacrylate. Commercially available copolymerizable emulsifiers of formula (I) include Maxemul® emulsifier, Sipomer® PAM emulsifier, Latemul® PD, and ADEKA Reasoap® PP-70.

[0135] A specific embodiment of the copolymerizable emulsifier of formula (II) is also known as alkyl sulfosuccinate allyl ester. The commercially available copolymerizable emulsifier of formula (II) is Trem® LF40.

[0136] Specific embodiments of the copolymerizable emulsifier of formula (III) are also referred to as branched unsaturated compounds. Commercially available copolymerizable emulsifiers of formula (III) are Adeka® Reasoap emulsifier and Hitenol® KH.

[0137] Specific embodiments of the copolymerizable emulsifier of formula (IV) are also known as polyoxyethylene alkylphenyl ether sulfate and polyoxyethylene mono- or stilbene phenyl ether sulfate. Commercially available copolymerizable emulsifiers of formula (IV) are Hitenol® BC and Hitenol® AR emulsifiers.

[0138] For other suitable anionic surfactants, see Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Vol. XIV / 1, Makromolekulare Stoffe [Macromolecular Substances], Georg-Thieme-Verlag, Stuttgart, 1961, pp. 192-208.

[0139] Preferably, the surfactant comprises at least one anionic emulsifier having at least one sulfate or sulfonic acid group. The at least one anionic emulsifier having at least one sulfate or sulfonic acid group may be the only type of anionic emulsifier. However, a mixture of at least one anionic emulsifier having at least one sulfate or sulfonic acid group and at least one anionic emulsifier having at least one phosphate or phosphonate group may also be used. In such mixtures, the amount of at least one anionic emulsifier having at least one sulfate or sulfonic acid group is preferably at least 50% by weight, based on the total weight of the anionic surfactants used in the process of the present invention. Specifically, the amount of anionic emulsifier having at least one phosphate or phosphonate group does not exceed 20% by weight, based on the total weight of the anionic surfactants used in the process of the present invention.

[0140] Preferred anionic surfactants are anionic emulsifiers (including mixtures thereof) selected from the following groups: - alkyl sulfates, especially salts of C8-C22-alkyl sulfates, especially alkali metal salts and ammonium salts; - ethoxylated monoesters of alkanols, especially ethoxylated C8-C22-alkanols (preferably having an ethoxylation degree (EO degree) in the range of 2 to 40), especially alkali metal salts; - ethoxylated monoesters of alkylphenols, especially ethoxylated C4-C18-alkylphenols (EO degree preferably 3 to 40) monoesters of alkylbenzene sulfonic acids, especially C4-C22-alkylbenzene sulfonic acids; and - mono- or disulfonated, alkyl-substituted diphenyl ethers, for example bis(phenylsulfonic acid) ethers having C4-C24-alkyl groups on one or both aromatic rings. - Polymerizable emulsifiers of formula (III).

[0141] Preferably, anionic emulsifiers (including mixtures thereof) are selected from the following groups: - alkyl sulfate esters, especially salts of C8-C22-alkyl sulfate esters, especially alkali metal salts and ammonium salts; - ethoxylated monoesters of alkanols, especially ethoxylated C8-C22-alkanols (preferably having an ethoxylation degree (EO degree) in the range of 2 to 40) of monoester salts, especially alkali metal salts; - mono- or disulfonated, alkyl-substituted diphenyl ethers, for example, bis(phenylsulfonic acid) ethers having C4-C24-alkyl groups on one or both aromatic rings - polymerizable emulsifiers of formula (III), wherein Y is SO3-.

[0142] In addition to the anionic surfactants mentioned above, surfactants may also include one or more nonionic surfactants, particularly selected from nonionic emulsifiers. Suitable nonionic emulsifiers are, for example, arylita- or aliphatic nonionic emulsifiers, such as ethoxylated mono-, di-, and trialkylphenols (EO degree: 3 to 50, alkyl: C4-C10), ethoxylated long-chain alcohols (EO degree: 3 to 100, alkyl: C8-C36), and polyethylene oxide / polypropylene oxide homopolymers and copolymers. These emulsifiers may include epoxy alkyl units copolymerized in a random distribution or in a block copolymer form. A highly suitable example is an EO / PO block copolymer. Preferred are ethoxylated long-chain alkanols, specifically those in which the alkyl C8-C30 has an average degree of ethoxylation of 5 to 100, and even more preferred are those having straight-chain C12-C20 alkyl groups with an average degree of ethoxylation of 10 to 50, as well as ethoxylated monoalkylphenols.

[0143] Based on the total amount of surfactant used in the process of the present invention, the surfactant used in the process of the present invention generally includes no more than 30% by weight, particularly no more than 20% by weight, of nonionic surfactant and particularly excludes any nonionic surfactant. A combination of at least one anionic surfactant and at least one nonionic surfactant may also be used. In this case, the weight ratio of the total amount of anionic surfactant to the total amount of nonionic surfactant is in the range of 99:1 to 70:30, specifically 98:2 to 75:25, and particularly in the range of 95:5 to 80:20.

[0144] Preferably, based on the monomer M to be polymerized, the amount of surfactant used should be in the range of 0.2 wt% to 5 wt%, particularly in the range of 0.3 wt% to 4.5 wt%. In multi-step emulsion polymerization, based on the total amount of polymerizable monomers in each step, the amount of surfactant used should generally be in the range of 0.2 wt% to 5 wt%, particularly in the range of 0.3 wt% to 4.5 wt%.

[0145] Preferably, at the same time as adding the monomer, most (i.e., at least 80%) of the surfactant used is added to the emulsion polymerization. Specifically, the monomer is added to the polymerization reaction solution in the form of an aqueous emulsion, the polymerization reaction solution containing at least 80% of the surfactant used for emulsion polymerization.

[0146] It has been found that free radical emulsion polymerization of monomer M can be advantageously carried out in the presence of seed latex. Seed latex is a polymer latex present in an aqueous polymerization medium prior to the initiation of polymerization of monomer M. Seed latex can help to better control particle size or the final polymer latex obtained in the free radical emulsion polymerization of the present invention.

[0147] In principle, each polymer latex can be used as a seed latex. For the purposes of this invention, a seed latex with relatively small polymer particle size is preferred. Specifically, the Z-average particle size of the polymer particles of the seed latex is preferably in the range of 10 nm to 80 nm, specifically 10 nm to 50 nm, as determined by dynamic light scattering (DLS) at 20°C (see below). Preferably, the polymer particles of the seed latex are prepared from an olefinic unsaturated monomer comprising at least 95% by weight (based on the total weight of the monomers forming the seed latex) one or more monomers selected from the group consisting of: C2-C10 alkyl acrylates (specifically ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethyl-hexyl acrylate), C1-C4 alkyl methyl acrylates (e.g., methyl methacrylate), monoolefinic unsaturated nitriles (e.g., acrylonitrile), and vinyl aromatic monomers as defined above (e.g., styrene), and mixtures thereof. Specifically, the polymer particles of seed latex are produced from an olefinic unsaturated monomer comprising at least 95% by weight (based on the total weight of the monomers forming the seed latex) one or more monomers selected from the group consisting of: C1-C4-alkyl methacrylates (e.g., methyl methacrylate), monoolefinic unsaturated nitriles (e.g., acrylonitrile), and vinyl aromatic monomers as defined above (e.g., styrene), and mixtures thereof.

[0148] For this purpose, seed latex is typically loaded into the polymerization vessel before the polymerization of monomer M begins. Specifically, the seed latex is loaded into the polymerization vessel, and then polymerization conditions are established (e.g., by heating the mixture to the polymerization temperature). It may be advantageous to load at least a portion of the free radical initiator into the polymerization vessel before adding monomer M. However, monomer M and free radical polymerization initiator may also be added to the polymerization vessel simultaneously.

[0149] Based on the total weight of the monomers in the monomer composition M to be polymerized, the amount of seed latex (in solid form) is generally in the range of 0.01% by weight to 10% by weight, preferably in the range of 0.05% by weight to 5% by weight, and specifically in the range of 0.05% by weight to 3% by weight.

[0150] The free radical aqueous emulsion polymerization of the present invention can be carried out at temperatures ranging from 0°C to 170°C. The temperatures used are typically in the ranges of 50°C to 120°C, typically 60°C to 120°C, and typically 70°C to 110°C. The free radical aqueous emulsion polymerization of the present invention can be carried out at pressures less than, equal to, or greater than 1 atm (atmosphere), and the polymerization temperature can exceed 100°C and can be up to 170°C. Monomer polymerization is typically carried out under ambient pressure, but it can also be carried out under high pressure. In this case, the pressure can be assumed to be 1.2, 1.5, 2, 5, 10, 15 bar (absolute value) or even higher. If the emulsion polymerization is carried out under reduced pressure, pressures of 950 mbar, typically 900 mbar, and typically 850 mbar (absolute value) are established. Advantageously, the free radical aqueous emulsion polymerization of the present invention is carried out under ambient pressure (about 1 atm) and oxygen is removed (for example) under an inert gas atmosphere (e.g., under nitrogen or argon).

[0151] The process for producing the polymer latex of the present invention can be single-stage polymerization or multi-stage emulsion polymerization. In single-stage polymerization, the total composition of monomer M supplied to the polymerization reaction under polymerization conditions remains the same or nearly the same, while in multi-stage emulsion polymerization, the total composition of monomer M supplied to the polymerization reaction under polymerization conditions changes at least once. Specifically, the theoretical glass transition temperature of the polymer formed in one stage differs from that of the polymer formed in another stage by at least 10°C, specifically at least 20°C or at least 40°C.

[0152] In specific group embodiments, the process of the present invention is implemented as a 2-stage emulsion polymerization, that is, the composition of the monomer supplied to the polymerization reaction changes once under polymerization conditions; or it is implemented as a 3-stage or 4-stage emulsion polymerization, that is, the composition of the monomer supplied to the polymerization reaction changes twice or three times under polymerization conditions.

[0153] Specifically, the aqueous emulsion polymerization is a multi-stage aqueous emulsion polymerization, comprising i. a first stage: subjecting a monomer composition Mi to aqueous emulsion polymerization to obtain a first-stage polymer latex, the monomer composition corresponding to a theoretical glass transition temperature Tgt(i) in the range of -25°C to +40°C, specifically in the range of -20°C to +20°C, according to the Fox equation; and ii. a second stage: subjecting a monomer composition Mii in the first-stage polymer latex to aqueous emulsion polymerization, wherein the monomer composition Mii corresponds to a theoretical glass transition temperature Tgt(ii) in the range of 50°C to 150°C, specifically in the range of 60°C to 120°C, according to the Fox equation; or alternatively comprising i. a first stage: subjecting a monomer composition Mi to aqueous emulsion polymerization to obtain a first-stage polymer latex, the monomer composition corresponding to a theoretical glass transition temperature Tgt(i) in the range of 50°C to 150°C, specifically in the range of 60°C to 120°C, according to the Fox equation; and ii. Second stage: The monomer composition Mii in the polymer latex of the first stage is subjected to aqueous emulsion polymerization, wherein the monomer composition Mii corresponds to the theoretical glass transition temperature Tgt(ii) in the range of -25°C to +40°C, specifically in the range of -20°C to +20°C, according to the Fox equation.

[0154] In the multi-stage aqueous emulsion polymerization, the monomer composition corresponding to the theoretical glass transition temperature in the range of -25°C to +40°C, and specifically in the range of -20°C to +20°C, preferably contributes 50 wt.-% to 95 wt.-%, more preferably 60 wt.-% to 90 wt.-%, of the total amount of monomer M, while the monomer composition corresponding to the theoretical glass transition temperature in the range of 50°C to 150°C, and specifically in the range of 60°C to 120°C, preferably contributes 5 wt.-% to 50 wt.-%, more preferably 10 wt.-% to 40 wt.-%.

[0155] In embodiments of a specific group, the aqueous emulsion polymerization is a multi-stage aqueous emulsion polymerization, comprising: i. a first stage: aqueous emulsion polymerization of a monomer composition Mi corresponding to a theoretical glass transition temperature Tgt(i) in the range of 50°C to 150°C, specifically in the range of 60°C to 120°C, according to the Fox equation, to obtain a first-stage polymer latex, wherein the monomer composition Mi comprises, based on the total weight of the monomer composition Mi, at least 0.5 wt% to 10 wt% of one monomer M4; ii. a second stage: aqueous emulsion polymerization of a monomer composition Mii in the first-stage polymer latex, wherein the monomer composition Mii corresponds to a theoretical glass transition temperature Tgt(ii) in the range of -25°C to +40°C, specifically in the range of -20°C to +20°C, according to the Fox equation, wherein the monomer composition Mii comprises, based on the total weight of the monomer composition Mii, at most 0.5 wt% of one or more monomers M4. Prior to the second stage of aqueous emulsion polymerization in step ii, the polymer latex obtained in step i is neutralized to a pH of at least pH 5.

[0156] In embodiments of this particular group, monomer composition Mi preferably contributes 5 wt.% to 50 wt.% of the total amount of monomer M, more preferably 10 wt.% to 40 wt.% of the total amount of monomer M, while monomer composition Mii preferably contributes 50 wt.% to 95 wt.% of the total amount of monomer M, more preferably 60 wt.% to 90 wt.% of the total amount of monomer M.

[0157] In embodiments of this particular group, the monomer composition Mi is preferably polymerized in the presence of a chain transfer agent as described below. The amount of chain transfer agent may be in the range of 0.05% by weight to 8% by weight, and specifically in the range of 0.1% by weight to 4% by weight, depending on the total amount of the monomer composition Mi.

[0158] The polymerization of monomer M may be carried out in the presence of a chain transfer agent, as appropriate. A chain transfer agent should be understood as a compound that transfers free radicals and reduces the molecular weight of the growing chain and / or controls chain growth during polymerization. Examples of chain transfer agents are aliphatic and / or aryliphatic halogen compounds, such as n-butyl chloride, n-butyl bromide, n-butyl iodide, dichloromethane, ethylene dichloride, chloroform, bromoform, bromotrichloromethane, dibromodichloromethane, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide; and organosulfur compounds, such as primary, secondary, or tertiary aliphatic thiols (e.g., ethanethiol, n-propanethiol, 2-propanethiol, n-butanethiol, 2-butanethiol, 2-methyl-2-propanethiol, n-pentanethiol, 2-pentanethiol, 3-pentanethiol, 2-methyl-2-butanethiol, 3-methyl-2-butanethiol, n-hexanethiol, 2-hexanethiol, 3-hexanethiol, 2-methyl-2-pentanethiol, 3-methyl-2-pentanethiol, 4-methyl-2-pentanethiol). 2-Methyl-3-pentanethiol, 3-methyl-3-pentanethiol, 2-ethylbutanethiol, 2-ethyl-2-butanethiol, n-heptanethiol and its isomers, n-octanethiol and its isomers, n-nonanethiol and its isomers, n-decanethiol and its isomers, n-undecanethiol and its isomers, n-dodecanethiol and its isomers, n-tridecanethiol and its isomers), substituted thiols (e.g., 2-hydroxyethylthiol), aromatic thiols (e.g., benzenethiol or o-, m-, or p-methylbenzenethiol), alkyl esters of thioglycolic acid (e.g., 2-ethylhexyl thioglycolic acid), alkyl esters of mercaptopropionate (e.g., octyl mercaptopropionate), and those described in Polymer Other sulfur compounds mentioned in Handbook, 3rd Edition, 1989, J. Brandrup and EH Immergut, John Wiley & Sons, Section II, pages 133-141; and aliphatic and / or aromatic aldehydes (e.g., acetaldehyde, propionaldehyde and / or benzaldehyde), unsaturated fatty acids (e.g., oleic acid), dienes with non-conjugated double bonds (e.g., divinylmethane or vinylcyclohexane) or hydrocarbons with readily extractable hydrogen atoms (e.g., toluene).

[0159] Alternatively, a mixture of chain transfer agents mentioned above that do not interfere with each other can be used. Based on the total amount of monomer M, the total amount of chain transfer agent used in the process of this invention typically does not exceed 2% by weight, specifically 1% by weight. However, it is possible that, during a certain period of the polymerization reaction, based on the total amount of monomer M added to the polymerization reaction during that period, the chain transfer agent added to the polymerization reaction may exceed 2% by weight and may be as high as 8% by weight, specifically up to 4% by weight.

[0160] It is generally advantageous to post-treat the aqueous polymer dispersion obtained when monomer M has completed polymerization to reduce the residual monomer content. This post-treatment is carried out chemically (e.g., by using a more efficient free radical initiator system to complete the polymerization reaction (referred to as post-polymerization)) and / or physically (e.g., by using steam or inert gas stripping of the aqueous polymer dispersion). The corresponding chemical and physical methods are well known to those skilled in the art – see, for example, EP-A 771328, DE-A 19624299, DE-A 19621027, DE-A 19741184, DE-A 19741187, DE-A 19805122, DE-A 19828183, DE-A 19839199, DE-A 19840586 and DE-A 19847115. The advantage of combining chemical and physical post-treatment is that it not only removes unconverted olefinic unsaturated monomers from aqueous polymer dispersions, but also removes other damaging volatile organic compounds (VOCs).

[0161] Because the polymer contained in the aqueous polymer dispersion may contain acidic groups from monomer M4 and, where appropriate, from the polymerization initiator, the aqueous polymer dispersion obtained by the process of this invention is usually neutralized before being formulated into a coating composition. Neutralizers are known to those skilled in the art to neutralize the acidic groups of the polymer after polymerization and / or during polymerization. For example, the neutralizer can be added in a combined feed form with the monomer to be polymerized or in a separate feed form. Suitable neutralizers include organic amines, basic hydroxides, and ammonium hydroxide. Specifically, neutralization is achieved by using ammonia or a basic hydroxide (e.g., sodium hydroxide or potassium hydroxide).

[0162] Additionally, a post-curing agent can be used to formulate the polymer latex of the present invention. Ideally, this post-curing agent (also known as a post-crosslinking agent) generates a crosslinking reaction during and / or after film formation by forming coordination or covalent bonds with reactive sites on the surface of polymer particles.

[0163] Suitable crosslinking agents for post-crosslinking are, for example, compounds having at least two functional groups selected from oxazoline, amino, aldehyde, aminooxy, carbodiimide, aziridinyl, epoxy, and acehydrazine groups, or derivatives or compounds having acetylacetyl groups. These crosslinking agents react with reactive sites in the polymer dispersion, wherein the polymer has complementary functional groups capable of forming covalent bonds with the crosslinking agent. Suitable systems are known to those skilled in the art.

[0164] Because the polymer contained in the polymer dispersion of the present invention has carboxyl groups, post-crosslinking can be achieved by using one or more polycarbodiimides to formulate the polymer dispersion, 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 the crosslinking is based on the reaction between the carboxyl groups of the polymer and the polycarbodiimide. This reaction typically produces covalent crosslinks primarily based on N-propylurea bonds (JW Taylor and DR Bassett, EJ Glass (ed.), Technology for Waterborne Coatings, ACS Symposium Series 663, Am. Chem. Soc., Washington, DC, 1997, Chapter 8, pp. 137–163).

[0165] Similarly, since the polymer particles contained in the polymer dispersion of the present invention have carboxyl groups derived from monomer M4, the suitable post-curing agent may also be a water-soluble or water-dispersible polymer with oxazoline groups (e.g., polymers described in US 5300602 and WO 2015 / 197662).

[0166] Post-crosslinking can also be achieved similarly to EP 1227116, which describes an aqueous two-component coating composition containing a binder polymer having carboxylic acid and hydroxyl functional groups and a multifunctional crosslinker having functional groups selected from isocyanate group, carbodiimide group, aziridinyl group and epoxy group.

[0167] If the polymer in the polymer dispersion (e.g., due to the use of monomer M5c, has ketone groups (e.g., diacetone acrylamide (DAAM)), then post-crosslinking can be achieved by using one or more diacetylhydrazines, and specifically aliphatic dicarboxylic acids (e.g., diacetylhydrazine adipic acid (ADDH)), to formulate the aqueous polymer dispersion, as described in US 4931494, US 2006 / 247367 and US 2004 / 143058. These components mainly react during and after film formation, but a certain degree of initial reaction may occur.

[0168] Other suitable agents for post-curing include - epoxy silanes for crosslinking carboxyl groups in the polymer; - dialdehydes (e.g., glyoxal) for crosslinking urea or acetoacetoxy groups (e.g., derived from monomers M5b and M5c as defined herein, specifically urea methacrylate or acetoacetoxy ethyl methacrylate); - di- and / or polyamines for crosslinking ketones or epoxy groups (e.g., derived from monomers M5c or M6b as defined herein); and - UV initiators, such as benzophenone (including benzophenone, 4-methoxybenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone), acetophenone (e.g., 2-hydroxy-2,2-dimethylacetophenone, 2-phenyl-2,2-dimethylacetophenone), cycloalkylphenyl ketones (e.g., 1-benzoylcyclohexane-1-ol (= 1-Hydroxycyclohexylphenyl ketone and benzoin and mixtures thereof, and specifically liquid mixtures (e.g., mixtures of 4-methylbenzophenone and benzophenone, mixtures of 2,4,6-trimethylbenzophenone and benzophenone, and mixtures of 1-hydroxycyclohexylphenyl ketone and benzophenone).

[0169] Suitable systems (e.g.) described in EP 355028, EP 441221, EP 0789724, US 5516453 and US 5498659 and / or commercially available (e.g., in the case of UV initiators from Omnirad and IGM Resins (e.g. Esacure TZM, Esacure TZT, Omnirad 4MBZ)).

[0170] This invention also relates to water-based coating compositions containing the polymer latex of this invention as a binder or as a co-binder. Specifically, this invention also relates to water-based coating compositions wherein the polymer latex is the sole binder or its amount accounts for at least 80% of the binder contained in the coating composition.

[0171] The water-based coating composition of the present invention can be formulated as a transparent coating or paint. In the latter case, in addition to the polymer latex, the water-based coating composition also contains at least one inorganic pigment, which imparts a white hue or color to the coating obtained when the substrate is coated using the water-based coating composition.

[0172] According to the definition in German standard DIN 55944:2003-11, the pigment used for the purposes of this invention is a practically insoluble, finely dispersed organic or preferably inorganic colorant. Examples of pigments specifically refer to inorganic pigments, such as white pigments (e.g., titanium dioxide, CI Pigment White 6); and also colored pigments, such as - black pigments, such as iron oxide black (CI Pigment Black 11), iron-manganese black, spinel black (CI Pigment Black 27), carbon black (CI Pigment Black 7); - colored pigments, such as chromium oxide, hydrated chromium oxide green; chrome green (CI Pigment Green 48); cobalt green (CI Pigment Green 50); ultramarine green; cobalt blue (CI Pigment Blue 28 and 36); ultramarine blue, iron blue (CI Pigment Blue 27), manganese blue, ultramarine violet, cobalt violet, manganese violet, iron oxide red (CI Pigment Red 101); cadmium sulfide selenide (CI Pigment Red 108); molybdenum red (CI Pigment Red 104); ultramarine red; - iron oxide brown, mixed brown, spinel-and corundum (CI Pigment Brown 24, 29 and 31), chrome orange; - Iron oxide yellow (CI Pigment Yellow 42); nickel titanium yellow (CI Pigment Yellow 53; CI Pigment Yellow 157 and 164); chromium titanium yellow; cadmium sulfide and zinc cadmium sulfide (CI Pigment Yellow 37 and 35); chrome yellow (CI Pigment Yellow 34), zinc yellow, alkaline earth metal chromates; antimony yellow (Naples yellow); bismuth vanadate (CI Pigment Yellow 184); - interference pigments, such as metallic effect pigments based on coated metal flakes, pearlescent pigments based on mica flakes coated with metal oxides, and liquid crystal pigments.

[0173] Water-based coating compositions may also contain one or more fillers. Examples of suitable fillers are aluminosilicates (e.g., feldspar), silicates (e.g., kaolin, talc, mica, magnesite), alkaline earth metal carbonates (e.g., calcium carbonate, magnesium carbonate, dolomite in the form of calcite or chalk), alkaline earth metal sulfates (e.g., calcium sulfate), silica, etc. In the coating compositions of the present invention, fine fillers are naturally preferred. Fillers can be used in the form of individual components. However, in practice, filler mixtures have been found to be particularly useful (e.g., calcium carbonate / kaolin, calcium carbonate / talc). Gloss paints typically contain only a small amount of very fine fillers or no fillers at all. Fillers may also contain matting agents that significantly impair gloss, as needed. Matting agents are generally transparent and may be organic or inorganic. Examples of matting agents are inorganic silicates, such as the Syloid® trademark from WR Grace & Company and the Acematt® trademark from Evonik GmbH. Organic matting agents can be obtained, for example, from BYK-Chemie GmbH under the Ceraflour® and Ceramat® trademarks and from Deuteron GmbH under the Deuteron MK® trademark.

[0174] The proportions of pigments and fillers in a water-based coating composition can be described by pigment volume concentration (PVC) in a manner known per se. PVC is expressed as a percentage of the ratio of pigment volume (VP) and filler volume (VF) in the dried coating film to the total volume (composed of binder volume (VB), pigment volume (VP), and filler volume (VF): PVC [%] = (VP + VF) × 100 / (VP + VF + VB).

[0175] If the water-based coating composition is formulated as a paint, it typically has a pigment volume concentration (PVC) of at least 5%, particularly at least 10%, and typically not exceeding 90%, specifically 85%. In preferred group embodiments, the PVC is not more than 60%, particularly 50%, and specifically in the range of 5% to 60% or 5% to 50%. However, the inventive effect of polymer dispersions is also manifested in varnishes, which typically have a pigment / filler content of less than 5% by weight (based on the varnish) and correspondingly less than 5% PVC. In yet another group of embodiments, the PVC is in the range of >60% to 90%, and specifically in the range of 65% to 85%.

[0176] According to one group of embodiments, the water-based coating composition of the present invention is designed as a paint containing a white pigment—that is, it comprises at least one white pigment and, where appropriate, one or more fillers. Specifically, the white pigment comprises titanium dioxide, preferably in the rutile form, and is combined, where appropriate, with one or more fillers. More preferably, for example, the coating composition of the present invention comprises a combination of a white pigment, more particularly preferably titanium dioxide in the rutile form, and one or more fillers (e.g., chalk, talc, or mixtures thereof).

[0177] In another preferred embodiment, the water-based coating composition of the present invention is designed as a clear coating or a wood stain formulation. Unlike paint, clear coatings are essentially free of pigments and fillers, while wood stains contain less filler, i.e., they have less than 5% PVC.

[0178] According to embodiments of a specific group, the present invention also relates to water-based coating compositions (hereinafter also referred to as water-based coating compositions) comprising: i) at least one water-based polymer latex as defined above; and ii) titanium dioxide pigment.

[0179] According to embodiments of another specific group, the present invention also relates to the use of waterborne polymer latex as a binder in waterborne coating compositions containing titanium dioxide pigments.

[0180] In the embodiments mentioned above, an aqueous polymer latex is combined with a TiO2 pigment slurry or paste. The TiO2 concentration of the aqueous TiO2 pigment slurry or paste used to prepare the aqueous coating composition is typically in the range of 30% to 85% by weight, typically 40% to 80% by weight, and each case is based on the total weight of the aqueous TiO2 pigment slurry or paste. The titanium dioxide pigment used to prepare the aqueous dispersion of the pigment slurry or paste can be any TiO2 pigment commonly used in coating compositions, and specifically in aqueous coating compositions. Typically, TiO2 pigments in which the TiO2 particles are preferably in the form of rutile are used. In another preferred embodiment, the TiO2 particles may also be coated, for example, with aluminum, silicon, and zirconium compounds.

[0181] Generally, the weight ratio of polymer to titanium dioxide pigment is in the range of ≥ 0.1:5.0 to ≤ 5.0:0.1; preferably, the weight ratio of polymer to titanium dioxide pigment is in the range of ≥ 0.5:5.0 to ≤ 5.0:0.5; more preferably, the weight ratio of polymer to titanium dioxide pigment is in the range of ≥ 0.5:3.0 to ≤ 3.0:0.5 and specifically in the range of ≥ 0.5:1.5 to ≤ 1.5:0.5.

[0182] Preferably, the titanium dioxide pigment has an average first-order particle size in the range of ≥ 0.1 µm to ≤ 0.5 µm, as determined by light scattering or electron microscopy.

[0183] Generally, the waterborne coating composition further includes at least one additive selected from the group consisting of: thickeners, defoamers, homogenizers, film-forming aids, biocides, wetting agents or dispersants, fillers and agglomerators.

[0184] Aqueous coating compositions can be easily prepared by mixing TiO2 pigment powder or an aqueous slurry or paste of TiO2 pigment with the aqueous polymer latex of the present invention, preferably by applying shear to the mixture, for example by using a solvent commonly used to prepare water-based paints. Alternatively, an aqueous slurry or paste of TiO2 pigment and the aqueous polymer latex of the present invention can be prepared and then incorporated into or mixed with other polymer latexes or any other polymer latex binders of the present invention.

[0185] The aqueous dispersion of the polymer composite can also be prepared by incorporating the aqueous polymer latex of the present invention as a binder or co-binder into an aqueous matrix formulation of paint containing TiO2 pigment, for example by mixing the aqueous polymer latex of the present invention with a pigment formulation containing other additives commonly used in paint formulations.

[0186] To stabilize TiO2 pigment particles in aqueous pigment slurries or pastes, mixing may be carried out in the presence of additives (e.g., dispersants) commonly used in aqueous pigment slurries or pastes, as appropriate. Suitable dispersants include (e.g., but not limited to) polyphosphates (e.g., sodium polyphosphate, potassium polyphosphate, or ammonium polyphosphate), alkali metal salts and ammonium salts of acrylic homopolymers or copolymers or maleic anhydride polymers, polyphosphonates (e.g., sodium 1-hydroxyethane-1,1-diphosphonate), and naphthalene sulfonates (especially their sodium salts).

[0187] The polymer concentration in the aqueous polymer latex used to prepare the aqueous dispersion of the polymer complex is generally in the range of 10% to 70% by weight, preferably 20% to 65% by weight and most preferably 30% to 60% by weight, each case being based on the total weight of the aqueous polymer latex.

[0188] In addition to the polymer latex and titanium dioxide pigment of the present invention and optional conventional binders, the waterborne coating composition may also contain one or more pigments different from the TiO2 pigments and / or fillers described above.

[0189] Preferably, the water-based coating composition includes at least one water-based polymeric latex as defined herein, further including a rheology modifier. Suitable rheology modifiers include associative thickener polymers and non-associative rheology modifiers. The water-based liquid composition preferably includes a thickener selected from the group consisting of associative thickeners and, where applicable, non-associative thickeners.

[0190] Associative thickener polymers are well known and usually described in scientific literature (e.g., EJ Schaller et al., "Associative Thickeners", Handbook of Coating Additives, Vol. 2 (ed. LJ Calbo), Marcel Decker 192, pp. 105-164; J. Bieleman, "PUR-Verdicker", Additives for Coatings (ed. J. Bielemann), Wiley 2000, pp 50-58). NiSAT thickener polymers of the HEUR and HMPE types are also described in patent literature (e.g., 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). In addition, associative thickener polymers are also commercially available.

[0191] Associative thickener polymers include anionic, acrylate-type thickener polymers, also known as HASE polymers (hydrophobically modified polyacrylate thickeners), which are copolymers of acrylic acid and alkyl acrylate monomers, wherein the alkyl group of the alkyl acrylate may have 6 to 24 carbon atoms. Associative thickener polymers also include nonionic associative thickeners, also known as NiSAT thickeners (nonionic synthetic associative thickeners), which are typically straight-chain or branched block copolymers having at least one internal hydrophilic moiety, specifically a polyether moiety, particularly at least one polyethylene oxide moiety, and two or more terminal hydrocarbon groups, each terminal hydrocarbon group having at least 4 carbon atoms, specifically 4 to 24 carbon atoms, such as straight-chain or branched alkyl groups having 4 to 24 carbon atoms, or alkyl-substituted phenyl groups having 7 to 24 carbon atoms. NiSAT thickener contains hydrophobically modified polyethylene oxide urethane rheology modifier (also known as HEUR or PUR thickener) and hydrophobically modified polyethylene oxide (also known as HMPE).

[0192] The amount of associative thickener polymer depends on the desired viscosity characteristics and is typically in the range of 0.05% to 2.5% by weight, specifically 0.1% to 2% by weight of thickener, and especially 0.2% to 2% by weight of latex paint.

[0193] Suitable non-associative rheology modifiers are specifically cellulose-based thickeners, especially hydroxyethyl cellulose and acrylate emulsion (ASE)-based thickeners. Among non-associative rheology modifiers, cellulose-based non-associative thickeners are preferred.

[0194] The total amount of thickener polymer depends on the desired viscosity characteristics and is typically in the range of 0.05% to 2.5% by weight, specifically 0.1% to 2% by weight of thickener, and especially 0.15% to 1.5% by weight, based on latex paint.

[0195] The waterborne coating composition of the present invention may also include conventional adjuvants. Conventional adjuvants are included (but not limited to) in a well-known manner depending on the type of coating, such as: - wetting agents or dispersants, - film-forming aids, also known as coalescing agents, - homogenizing agents, - UV stabilizers, - biocides and - defoamers / degassing agents.

[0196] Suitable wetting or dispersing agents include, for example, sodium polyphosphate, potassium polyphosphate or ammonium polyphosphate, alkali metal salts and ammonium salts of acrylic acid copolymers or maleic anhydride copolymers, polyphosphonates (e.g., sodium 1-hydroxyethane-1,1-diphosphonate) and naphthalene sulfonates (especially their sodium salts).

[0197] Suitable film-forming aids are solvents and plasticizers. Unlike solvents, plasticizers have low volatility and preferably a boiling point above 250°C at 1013 mbar, while solvents have higher volatility than plasticizers and preferably a boiling point below 250°C at 1013 mbar. Suitable film-forming aids are, for example, petroleum ethers, pine oil, propylene glycol, ethylene glycol, butanediol, butylene glycol acetate, butylene glycol diacetate, butyl diethylene glycol, butyl carbitol, 1-methoxy-2-propanol, 2,2,2-trimethyl-1,3-pentanediol monoisobutyrate (Texanol®), and glycol ethers and esters available from, for example, BASF SE (under the names Solvenon®, Lusolvan®, and Loxanol®) and Dow (under the trade name Dowanol®). Based on the overall formulation, its amount is preferably < 5% by weight and more preferably < 1% by weight. The formulation may also be completely free of film-forming aids. If the coating composition contains film-forming aids, such film-forming aids are preferably selected from plasticizers. Typically, coating compositions do not require any film-forming aids.

[0198] Other suitable adjuvants and components (e.g.) are described in the following literature: J. Bieleman, "Additives for Coatings", Whiley-VCH, Weinheim 2000; TC Patton, "Paint Flow and Pigment Dispersions", 2nd edition, John Whiley & Sons 1978; and M. Schwartz and R. Baumstark, "Water based Acrylates for Decorative Coatings", Curt R. Vincentz Verlag, Hanover 2001.

[0199] The water-based coating composition of the present invention can also be formulated as a low-VOC paint. In this case, based on the total amount of the water-based coating composition, the concentration of volatile compounds in the coating composition is preferably less than 0.1 wt.-%, more preferably less than 0.05 wt.-%. The volatile compounds in this invention refer to compounds with a boiling point of less than 250°C at 1013 mbar.

[0200] The water-based coating composition of the present invention is particularly suitable for coating wooden substrates (e.g., wood or wood-based materials). The water-based coating composition of the present invention is particularly suitable for use in architectural coatings, i.e., for coating exterior or interior parts of buildings. In this case, the substrate can be a mineral substrate, such as plaster, gypsum, plasterboard or concrete, wood, wood-based materials, metal, wallpaper or plastic (e.g., PVC).

[0201] The water-based coating composition can be applied to the substrate to be coated in a conventional manner, such as by brush or roller, by spraying, by dipping, by rolling or by sticking onto the desired substrate. Preferred application is by brush and / or by roller.

[0202] Typically, the substrate is coated in the following manner: firstly, the water-based coating composition of the present invention is coated onto the substrate, and then the water-based coating thus obtained is subjected to a drying step, particularly in a temperature range of ≥ -10°C to ≤ +50°C, advantageously ≥ +5°C to ≤ +40°C and particularly advantageously ≥ +10°C to ≤ +35°C.

[0203] Substrates coated with the water-based coating composition of the present invention exhibit excellent resistance to whitening when exposed to water or weathering conditions. Furthermore, when containing two or more polymer phases, the coating exhibits high anti-blocking properties. However, coatings obtained using the coating composition of the present invention are less prone to the cracking commonly observed when coating wooden substrates with water-based coating compositions. In addition, they are less prone to aging and do not exhibit undesirable viscosity increases during storage.

[0204] The invention is illustrated by the following non-limiting examples.

[0205] 1. Abbreviations: ADDH: Diazide adipic acid AM: Acrylamide AMA: Allyl methacrylate AS: Acrylic acid DAAM: Diacetone acrylamide DLS D[v, 4.3] value as determined by dynamic light scattering EHA: 2-ethylhexyl acrylate Area % Area percentage FuselA: Fusel alcohol acrylate i-BuA: Isobutyl acrylate MAS: Methacrylate MMA: Methyl methacrylate MeHQ: 4-Methoxyphenol (hydroquinone monomethyl ether) MEMO: 3-Methylacryloxypropyltrimethoxysilane n-BuA: n-Butyl acrylate ppphm: Fraction / 100 monomers PVC Pigment / volume concentration PTZ Phenythiazide RH: Relative humidity RT: Room temperature (22-23℃) rpm: Revolutions / minute S: Styrene SC: Solid content UMA: 25% solution of imidazolin-2-one-1-yl-ethyl methacrylate in methyl methacrylate wt%: weight % Here and below, the terms "room temperature" and "ambient temperature" mean a temperature in the range of 22-23°C.

[0206] 2. Analysis of Polymer Latex 2.1 Solids Content The solids content was determined by drying a specified amount of aqueous polymer dispersion (approximately 2 g) to a constant weight (2 hours) in an aluminum crucible with an inner diameter of approximately 5 cm at 130°C in a drying oven. Two separate measurements were performed. The values ​​reported in the examples are the average of the two measurements.

[0207] 2.2 Unless otherwise stated, the average particle size of the polymer latex is determined by using Malvern HPPS with dynamic light scattering (DLS) as described above.

[0208] The weight-average particle size of the polymer latex can also be determined by HDC. Measurements were performed using a PL-PSDA particle size analyzer (Polymer Laboratories, Inc.). A small amount of polymer latex sample was injected into an aqueous eluent containing an emulsifier to obtain a concentration of approximately 0.5 g / L. The mixture was aspirated through a glass capillary approximately 15 mm in diameter filled with polystyrene spheres. Due to the hydrodynamic diameter, smaller particles can spatially enter slower-flowing regions within the capillary, thus, on average, smaller particles experience slower elution flow. Finally, fractionation was monitored using a V detector, which measures extinction at a fixed wavelength of 254 nm.

[0209] 2.3 Brookfield viscosity The viscosity was measured at 20°C using the standard method DIN EN ISO 3219:1994, using a Brookfield RV type laboratory viscometer with a No. 4 or No. 5 spindle at 100 rpm.

[0210] 2.4 Glass transition temperature Tg The glass transition temperature was determined by DSC method (differential scanning calorimetry, 20 K / min, midpoint measurement, DIN 53765:1994-03) using a DSC instrument (Q 2000 series from TA Instruments).

[0211] 3. Emulsifiers, monomers, seed latex emulsifier 1: 45% bw aqueous solution of sodium 12-alkyl diphenyl oxide disulfonate (Dowfax® 2A1) emulsifier 2: 20% wt% aqueous solution of ethoxylated C16 / C18 alkanol with 18 EO emulsions (Lutensol® AT 18) emulsifier 3: 27% wt% aqueous solution of sodium lauryl ether sulfate (Disponil® FES 27) emulsifier 4: 15% wt% aqueous solution of sodium dodecyl sulfate (Disponil® SDS 15) emulsifier 5: 25 wt% aqueous solution of sodium salt of ethoxylated alkyl glycerol allyl ether of formula (III) with degree of ethoxylation = 10 (Adeka Reasoap SR-1025) emulsifier 6: 20% wt% aqueous solution of ethoxylated isocyl 13 alkanol with 8 EO emulsions (Lutensol TO82) seed latex 1: Polyacrylate latex seed latex 2 with a solid content of 33.00% by weight and a D[v, 4.3] value of 30 nm: Polystyrene latex sulfinate sodium hydroxymethanesulfinate (Rongalit® C) with a solid content of 33.00% by weight and a D[v, 4.3] value of 30 nm: Urea ethyl methacrylate (UMA): 25 wt% solution of imidazoline-2-one-1-yl-ethyl methacrylate in methyl methacrylate Sipomer® PAM 100: Phosphate half ester of hydroxyethyl methacrylate Isobutyl acrylate: Isobutyl acrylate with 57% biochar, obtained from BCH Brühl-Chemikalien Handel GmbH Isoamyl acrylate See below: Mixture of 2-methylbutyl acrylate and 3-methylbutyl acrylate in a 1:4 ratio of bioamyl acrylate - See below: Fusel oil acrylate: Acrylic acid is synthesized by esterification of fusel oil (purified by distillation), with 63% biochar; it contains approximately 87% isoamyl acrylate (a mixture of 2-methyl and 3-methyl-butyl isomers) + 10% isobutyl acrylate – the production process is described in the following scheme.

[0212] Scheme for producing fusel oil acrylate: 464 g of fusel oil (containing 10.5 wt% water and 89.5 wt% organic fraction, which is composed of a mixture of 12.4 wt% isobutanol and 80.0 wt% 2-methylbutanol and 3-methylbutanol) obtained as a side stream from bioethanol production, 400 mL of cyclohexane, 4.5 g of stabilizer solution (composed of 3.33 wt% MeHQ and 8.33 wt% 50 wt% hypophosphoric acid), and 3.5 g of 5 wt% copper(II) acetate solution were filled into a 2 L 4-necked flask equipped with a crescent stirrer, a water separator with a reinforced condenser, a gas feed tube, and a thermometer. 377.5 g of glacial acrylic acid (stabilized with 200 ppm MeHQ) and 28.5 g of p-toluenesulfonic acid monohydrate were added. The water separator was filled with cyclohexane.

[0213] The reaction mixture was then heated. Water was separated and air was introduced simultaneously at a bath temperature of 110°C. 160 g of water was distilled off. After a reaction time of 5.5 h, the mixture was cooled. 400 mL of water was added to the reaction mixture at an internal temperature of 50°C.

[0214] After separating the aqueous phase, a mixture of 375 mL of water and 150 mL of 12.5 wt% NaOH aqueous solution was added. After separating the aqueous phase, the organic phase was washed with 500 mL of 15 wt% NaCl aqueous solution. 877 g of crude solution was obtained, to which 0.9 g of phenthiazide was added, and the solution was concentrated using a rotary evaporator at 60 °C and 100 mbar to 65 mbar. The product was then distilled off at a bath temperature of 70 °C and a pressure of 20 mbar. 491.2 g of fusel oil acrylate was obtained and stabilized with 100 mg MeHQ. The product was clear and colorless and analyzed by gas chromatography. It contained a mixture of 11.5 area % isobutyl acrylate and 84.0 area % 2-methylbutyl acrylate and 3-methylbutyl acrylate (in a 20:80 ratio), as determined by 1H NMR.

[0215] Scheme for producing isoamyl acrylate: 1058 g of isoamyl alcohol (petrochemically derived), 823 g of cyclohexane, 11.4 g of stabilizer solution (composed of 3.33 wt% MeHQ and 8.33 wt% of 50 wt% hypophosphoric acid), and 8.4 g of 5 wt% copper(II) acetate solution were placed in a heated 4 L double-walled glass reactor equipped with a thermal sensor, anchor stirrer, water separator, enhanced condenser, and air feed. Then, 951 g of glacial acrylic acid (stabilized with 200 ppm MeHQ) was added. 95.4 g of 65% p-toluenesulfonic acid was added and heating was carried out. Water was distilled at a bottom temperature of 82°C to 101°C.

[0216] 278 mL of water with a water content of 95.5% was separated. The reaction was terminated after 5.5 h. After cooling, the reaction mixture was first extracted with 700 mL of water, then with a mixture of 500 mL of water and 400 g of 12.5% ​​NaOH solution, and then extracted again with 800 mL of water, separating the aqueous phase in each case. After the last phase separation, 1 g of MeHQ was added to the organic phase, and then partially distilled at a pressure of 230 mbar to 50 mbar. The internal temperature was increased from 44 °C to 81 °C. 1532 g of isoamyl acrylate with a GC purity of 99.1% by area and a color number of 5 (Hazen) was obtained and stabilized with 100 ppm MeHQ.

[0217] Scheme for producing bio-amyl acrylate: Ethyl acrylate (2555g), MeHQ (3.6g), phenothiazine (1.5g), and 1000g of isoamyl alcohol (obtained by the side stream from fractionated bioethanol, a mixture of 2-methylbutanol and 3-methylbutanol in a ratio of 1:4, as determined by 1H NMR) were introduced into a heated 4L double-walled glass reactor equipped with a heated lid, a 3-stage cross-blade stirrer, a 50 cm column (filled with Montz A3-750), a cooler, a phase separator, a thermal sensor, and a gas inlet pipe, and heated with rare air feed and stirring. Tetraisopropoxide titanium (36.06g) was added at an internal temperature of 70°C.

[0218] After boiling had begun, a reflux ratio of 5:1 (R:D) was used to begin extraction. Ethyl acrylate was fed fractionally to the bottom over the first 4 hours, corresponding to the amount of distillate. Over 4 hours, 111 g of PTZ / ethanol solution (0.01 wt%) was added to the top of the column. Bottom samples were taken at regular intervals and analyzed by gas chromatography to monitor reaction progress. Over the next 6 hours, the pressure was gradually reduced to 550 mbar and the reflux ratio was gradually adjusted to 2:5 (R:D). Fractionation of ethyl acrylate followed by the desired product was initiated at a conversion rate >99%. The pressure was further reduced to 80 mbar. Fractions with a purity >98% were combined. 1272 g of bio-amyl acrylate (a 1:4 mixture of 2-methylbutyl acrylate and 3-methylbutyl acrylate) with a purity of 99.2% was obtained. The product was stabilized using 100 ppm MeHQ.

[0219] 4. Preparation Examples 4.1 Comparative Examples C1 to C2 and Invention Examples D1 to D4: Emulsion A was prepared by mixing 345 g of water, 8.2 g of acrylic acid, 18.9 g of acrylamide, 8.7 g of emulsifier 1, 12.6 g of emulsifier 2 and the individual amounts of monomers given in Table 1.

[0220] Initiator solution I was prepared by dissolving 0.9 g of sodium peroxydisulfate in 12.7 g of deionized water.

[0221] An oxidizing solution O was prepared by dissolving 0.5 g of third butyl hydroperoxide in 5 g of deionized water.

[0222] A reducing solution R was prepared by dissolving 0.9 g of sodium sulfite in 7 g of deionized water (mixed with 0.4 g of acetone).

[0223] 182 g of deionized water and 17 g of emulsifier 4 were loaded into a reactor vessel equipped with a stirrer and three separate supply lines, and the vessel was preheated to 95°C. After reaching 95°C, 3.3% of emulsion A and 25% of initiator solution I were supplied to the vessel, and the mixture was stirred at 95°C for 10 minutes. Subsequently, the remaining portion of emulsion A was supplied to the reactor vessel over a period of 120 minutes while maintaining the 95°C. Simultaneously with the addition of emulsion A, the remaining portion of initiator solution I was supplied to the reactor vessel via separate supply lines over a period of 120 minutes. After the addition of emulsion A and initiator solution I was completed, stirring was continued at 95°C for another 15 minutes. Then, the vessel was cooled to 90°C, and 2.7 g of ammonia (25% wtaq) diluted with 4.0 g of water was added to the vessel. Subsequently, over a period of 60 minutes, oxidizing solution O and reducing solution R were simultaneously supplied to the reactor vessel via a separate supply line. After the addition of the oxidizing and reducing solutions was complete, the vessel was cooled to room temperature and 2.4 g of ammonia (25% wtaq) diluted with 15 g of water was added.

[0224] 4.2 Comparative Example C3 and Invention Examples D5 and D6: Emulsion A was prepared by mixing 265 g of water, 13 g of acrylic acid, 13 g of acrylamide, 16 g of emulsifier 3, 7 g of emulsifier 2 and the individual amounts of monomers given in Table 1.

[0225] Initiator solution I was prepared by dissolving 7.65 g of sodium peroxydisulfate in 101.57 g of deionized water.

[0226] An oxidizing solution O was prepared by dissolving 2.52 g of third butyl hydroperoxide in 22.67 g of deionized water.

[0227] A reducing solution R was prepared by dissolving 1.44 g of sodium sulfite in 15.36 g of deionized water (mixed with 0.85 g of acetone).

[0228] 265 g of deionized water and 30 g of seed latex 1 were loaded into a reactor vessel equipped with a stirrer and three separate supply lines, and the mixture was preheated to 83°C. After reaching the temperature of 83°C, emulsion A was supplied to the reactor vessel over a period of 120 minutes while maintaining the temperature at 83°C. Simultaneously with emulsion A, the remaining portion of the initiator solution I was supplied to the reactor vessel via separate supply lines over a period of 120 minutes. After the addition of emulsion A and the initiator solution was completed, the reaction mixture was stirred at 83°C for another 20 minutes.

[0229] Thereafter, the oxidizing solution O and the reducing solution R were simultaneously supplied to the reactor vessel via separate feed lines over a period of 60 minutes at 83°C. After the addition of the oxidizing and reducing solutions was completed, the vessel was cooled to room temperature and 3 g of ammonia solution (25%) and 15 g of water were added. Table 1 monomer C1 D1 D2 C2 D3 D4 C3 D5 D6 MMA [g] 464.3 382.0 285.5 465.4 362.9 430.0 257.4 222.9 140.3 n-BuA [g] 0 0 0 396.3 0 0 445.4 233.5 0 EHA [g] 397.5 213.2 0 0 0 0 0 0 0 S [g] 0 0 0 0 0 0 141.0 141.0 144.3 i-BuA [g] 0 266.5 576.3 0 498.9 0 0 264.4 577.2 FuselA [g] 0 0 0 0 0 431.8 0 0 0 SC [wt%] 48.5 48.1 47.9 49.8 49.9 48.6 52.8 52.7 52.8 pH 8.5 8.6 8.7 9.6 9.4 7.2 7.6 7.4 7.2 DLS [nm] 85 85 82 107 110 98 131 129 130 Tg (Fox) [℃] 11 10 12 twenty three twenty two twenty three 16 15 16 %C (Biological) [Calculated value] 1) 0% 18% 39% 0% 34% 32% 0% 17% 36% %C (Biological) [Measurement Value] 2) nd 18% 38% 0% 34% 32% nd nd nd 1) The theoretical relative amount of biochar in the compound latex, calculated from the reported amount of biochar in isobutanol (the value can be experimentally obtained by mass spectrometry using a 12C / 14C ratio). 2) The measured relative amount of biochar in the compound latex, as determined according to ASTM D6866-18 (Method B); measurements were performed at the Curt-Engelhorn Center for Archaeometry (Mannheim, Germany).

[0230] 4.3 Comparative Example C4 586.0 g of deionized water, 13.2 g of emulsifier 5, and 20.8 g of 3 wt% tetrasodium pyrophosphate aqueous solution were charged into a polymerization vessel equipped with a metering device and temperature control at 20°C to 25°C (room temperature) and a nitrogen atmosphere. This initial charge was heated to 80°C with stirring. At this temperature, a homogeneous solution of 3.0 g sodium persulfate in 39.9 g of deionized water was added, and the mixture was stirred at 80°C for 2 minutes. Subsequently, emulsion feed 1 was added over a 45-minute process, while maintaining the temperature at 80°C. After the addition of emulsion feed 1 was complete, polymerization continued at 80°C for 10 minutes. Then, 26.9 g of 25 wt% ammonia aqueous solution (the amount required to completely neutralize the methacrylic acid from emulsion feed 1) and 3.7 g of deionized water were added, and the mixture was stirred for 10 minutes.

[0231] Emulsion Feed 1 (homogeneous mixture): 139.7 g deionized water, 4.4 g emulsifier 5, 34.0 g methacrylic acid, 27.2 g ureoethyl methacrylate, 210.8 g methyl methacrylate, 34.0 g n-butyl acrylate, 170.0 g 20 wt% aqueous solution of diacetone acrylamide and 15.7 g 2-ethylhexyl thioglycolic acid.

[0232] Then emulsion feed 2 is added. After 45 minutes, when 50% of this feed is added, another 45 minutes are taken to add a homogenized solution of 0.5 g sodium persulfate in 6.6 g deionized water; the total supply time of emulsion feed 2 is 90 minutes.

[0233] Emulsion Feed 2 (homogeneous mixture): 188.4 g deionized water, 7.6 g emulsifier 5, 198.0 g n-butyl acrylate, 224.4 g 2-ethylhexyl acrylate, and 237.6 g methyl methacrylate

[0234] After the addition of emulsion feed 2, the polymerization mixture was further reacted at 80°C with stirring for 30 minutes. Then, 130.8 g of deionized water was added and stirring was continued at 70°C for another 90 minutes. The resulting aqueous polymer dispersion was then cooled to room temperature. At room temperature, 141.7 g of a 12 wt% aqueous solution of adipamide was added. Finally, the dispersion was filtered through a 125 μm filter.

[0235] The resulting aqueous polymer dispersion has a solids content of 42.9 wt%. After dilution with deionized water, the aqueous polymer dispersion has a weight-average particle size of 37 nm (measured by HDC).

[0236] 4.4 Examples D7 to D14 of the Invention Similar to Example C4, the polymer latexes of Examples D7 to D14 of the Invention are prepared by using individual relative amounts (given in pphm) instead of the monomer amounts in feeds 1 and 2, and are summarized in Table 2. Table 2 C4 D7 D8 D9 D10 D11 D12 D13 D14 Feed 1 nBuA 3.4 3.4 3.4 3.4 3.4 0 0 0 0 i-BuA 0 0 0 0 0 4.1 4.1 4.1 4.1 MMA 21.1 21.1 21.1 21.1 21.1 20.4 20.4 20.4 20.4 MAS 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 DAAM 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4 UMA 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 2.7 Tg (Fox) [℃] 91 91 91 91 91 92 92 92 92 Feed 2 EHA 22.5 19.1 16.5 2.6 7.9 19.1 16.5 2.6 7.9 nBuA 19.5 0 0 0 0 0 0 0 0 i-BuA 0 29.2 31.2 54.4 46.4 29.2 31.2 45.4 46.4 n-BMA 0 0 3.3 17.5 0 0 3.3 17.5 0 S 0 0 0 0 6.6 0 0 0 6.6 MMA 23.5 17.2 14.5 0 4.6 17.2 14.5 9 4.6 AMA 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Tg (Fox) [℃] -10 -10 -9 -11 -11 -10 -9 -11 -11 Polymer latex SC [wt%] 42.9 42.5 42.1 42.8 42.4 42.7 42.5 42.4 42.2 HDC [nm] 37 35 36 40 41 48 45 51 52 pH 7.9 8.1 8.2 8.1 8.1 8.2 8.2 8.1 8.1 BF 1) [mPas] 664 612 512 500 384 804 568 460 432 bio-C 2) [%] 0 17 18 27 27 20 twenty one 29 29 1) Rookfield viscosity 2) io-C: The theoretical relative amount of bio-carbon in polymer latex (this value can be experimentally determined by mass spectrometry using the 12C / 14C ratio).

[0237] 4.5 Comparative Example C5 In a polymerization vessel equipped with a metering device and controlled at 22°C, 341.9 g of deionized water and 55.0 g of emulsifier 4 were added under a nitrogen atmosphere and heated to 87°C while stirring. At 80°C, 43.0 g of feed 2 and 3.2 g of 7% bw sodium peroxydisulfate aqueous solution were added, and the mixture was further heated to 87°C. After 5 minutes, feeds 1 and 2 (remaining amounts) were added and metered into the reactor vessel over 120 minutes. At the end of the addition of feeds 1 and 2, post-polymerization was carried out for 5 minutes. Then, feeds 3 and 4 were metered into the reactor vessel over 45 minutes.

[0238] Feed 1: 13.7 g 7% bw sodium persulfate aqueous solution

[0239] Feed 2 (including the following emulsions): 526.1 g Deionized water 36.7 g Emulsifier 4 8.0 g Acrylic acid 9.0 g 50% BW acrylamide aqueous solution 313.0 g Methyl methacrylate 448.7 g 2-ethylhexyl acrylate 42.5 g 25% BW solution of urea methacrylate in methyl methacrylate

[0240] Feed 3: 5.1 g 7% bw sodium persulfate aqueous solution

[0241] Feed 4 (including the following emulsions): 272.9 g deionized water 13.9 g emulsifier 4 8.0 g acrylic acid 42.5 g 25% bw solution of urea methacrylate in methyl methacrylate 232.9 g methyl methacrylate

[0242] After the addition of feeds 3 and 4, the polymerization mixture was reacted at 87°C for 30 minutes; then 5.3 g of 25% BW ammonia solution and 55.4 g of deionized water were added. The mixture was cooled to 82°C and stirred for 60 minutes. Meanwhile, 22.9 g of 7.7% BW hydrogen peroxide solution and 22.8 g of 6.8% BW L-ascorbic acid solution were metered into a reactor vessel. Then, 15.4 g of 7.1% BW ammonia solution was added; the mixture was cooled to 22°C and the aqueous polymer dispersion was filtered through a 125 µm filter.

[0243] The obtained polymer latex has a solids content of 44.2%, a pH value of 7.7, and an average particle size of 68 nm (according to HDC).

[0244] 4.6 Examples D15 to D22 of the Invention Similar to Example C5, the polymer latexes of Examples D15 to D22 of the Invention are prepared by using individual relative amounts (given in pphm) instead of monomer amounts, and are summarized in Table 3. Table 3 C5 D15 D16 D17 D18 D19 D20 D21 D22 Feed 1 EHA 40.8 0 25 0 0 3.5 5.0 0 0 i-BuA 0 63.5 25.0 60.0 57.5 55.0 50.0 0 0 FuselA 49.5 60.0 MMA 28.5 5.9 19.4 9.4 11.9 10.9 14.4 19.9 9.4 ALL 3.9 3.9 3.9 3.9 3.9 3.9 3.9 3.9 3.9 AS 0.7 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 AM 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Tg (Fox) [℃] -4 -9 -6 -4 -1 -4 0 -3 -20 Feed 2 MMA 21.2 24.9 24.9 24.9 24.9 24.9 24.9 24.9 24.9 UMA 3.9 0 0 0 0 0 0 0 0 AS 0.7 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 Tg (Fox) [℃] 114 119 119 119 119 119 119 119 119 polymer latex SC [wt%] 44.2 44.2 44.2 44.8 44.3 45.0 44.8 44.2 44.7 HDC [nm] 68 74 77 77 77 74 77 77 77 pH 7.7 8.4 8.3 8.1 8.2 8.2 8.3 8.4 8.3 BF 1) [mPas] 260 300 270 300 270 304 230 280 272 bio-C 2) [%] 0 38 15 36 34 33 30 33% 39% %C-bio [Measurement value] 3) 1% nd nd 37% nd nd nd 34% 40% 1) F: Brookfield viscosity at 20°C 2) io-C: Theoretical relative amount of bio-carbon in polymer latex (value can be experimentally determined by mass spectrometry using the 12C / 14C ratio) 3) C-bio [measured value]: Measured relative amount of bio-carbon in polymer latex, as determined according to ASTM D6866-18 (Method B).

[0245] 4.6 Comparative Example C6 At room temperature and under a nitrogen atmosphere, 145.9 g of deionized water and 0.8 g of 33 wt.% polystyrene seed latex 2 were added to a polymerization vessel equipped with a metering device and temperature control. This initial addition was heated to 85°C with stirring. Once this temperature was reached, 7.1 g of sodium persulfate in a 7 wt.% solution in deionized water was added and the mixture was stirred at 85°C for 5 minutes.

[0246] Subsequently, emulsion feed 1 was added and the process was counted over 113 minutes, while maintaining a temperature of 85°C. At the same time, a 7 wt.% solution of 21.4 g of sodium persulfate in deionized water was added to the polymerization vessel over a 180-minute time period.

[0247] Emulsion Feed 1 (homogeneous mixture): 155.0 g deionized water, 13.4 g emulsifier 3, 149.1 g n-butyl acrylate, 59.0 g 2-ethylhexyl acrylate, 166.0 g styrene, and 1.0 g MEMO. Immediately after Emulsion Feed 1 has been supplied, Emulsion Feed 2 is added and counted after a 37-minute process.

[0248] Emulsion Feed 2 (Homogeneous Mixture): 52.5 g deionized water, 4.5 g emulsifier 3, 5.0 g Sipomer® PAM 100, 49.7 g n-butyl acrylate, 19.6 g 2-ethylhexyl acrylate, and 50.6 g styrene.

[0249] After the addition of emulsion feed 2, 6.1 g of deionized water was added and the polymerization mixture was further reacted at 85°C with stirring for 30 minutes. After partial neutralization with 0.8 g of 25 wt.% ammonia solution, 16.3 g of deionized water was added and stirring was continued at 85°C for another 5 minutes. Subsequently, 15.0 g of 10 wt.% tributyl hydroperoxide aqueous solution and 12.2 g of 13 wt.% acetone bisulfite aqueous solution were added simultaneously over a process of 120 minutes. 90 minutes after the start of this chemical deodorization step, a 10 wt.% solution of 14.5 g of sodium hydroxide in deionized water was added to the mixture over 30 minutes. The resulting aqueous polymer dispersion was then cooled to room temperature and 15.8 g of rinse water was added. Finally, the dispersion was filtered through a 125 μm filter.

[0250] The resulting aqueous polymer dispersion has a solids content of 51.7 wt%. After dilution with deionized water, the aqueous polymer dispersion has a weight-average particle size of 338 nm (measured by HDC).

[0251] 4.7 Invention Example D23 Similar to the scheme of Example C6, the polymer latex of Invention Example D23 is prepared by using individual relative amounts (given in pphm) instead of monomer amounts, and is summarized in Table 4. Table 4: monomer C6 D23 n-BuA [g] 198.8 0 EHA [g] 78.6 0 S [g] 216.6 139.3 i-BuA [g] 0 354.8 SC [wt%] 51.7 51.3 pH 7.6 7.4 DLS [nm] 335 319 Tg (Fox) [℃] 3 5 bio-C 1) [%] 0% 37% 1) io-C: The theoretical relative amount of bio-carbon in polymer latex (the value can be experimentally determined by mass spectrometry using the 12C / 14C ratio).

[0252] 4.8 Example D24 855 g of deionized water and 95.5 g of seed latex 2 were charged into a reactor equipped with a stirrer, temperature control, nitrogen inlet, and several injection possibilities. The reaction mixture was purged with nitrogen and heated to 85°C. At 85°C, 17.3 g of feed 2 was added. After 5 min, feed 1 and feed 2 were added over 180 min. Feed 1: 1345.2 g deionized water, 64.7 g emulsifier 1, 72.8 g emulsifier 6, 24.3 g acrylic acid, 48.5 g 50 wt% acrylamide aqueous solution, 1425.9 g isobutyl acrylate, and 950.6 g methyl methacrylate. Feed 2: 69.3 g sodium persulfate aqueous solution (7 wt%). The reaction mixture was post-polymerized at 85°C for 30 min. Then feed 3 and feed 4 were added over 60 min. Feed 3: 24.3 g of tert-butyl hydroperoxide aqueous solution (10 wt%). Feed 4: 21.8 g of sulfinate aqueous solution (10 wt%). The reaction mixture was then cooled to ambient temperature and neutralized to pH 8-9 using sodium hydroxide aqueous solution. Tg (dried dispersion): 21°C. Average particle size (DLS): 130 nm. Solids content: 46.1 wt%.

[0253] 4.9 Comparative Example C7 855 g of deionized water and 95.5 g of seed latex 2 were charged into a reactor equipped with a stirrer, temperature control, nitrogen inlet, and several injection possibilities. The reaction mixture was purged with nitrogen and heated to 85°C. At 85°C, 17.3 g of feed 2 was added. After 5 min, feed 1 and feed 2 were added over 180 min. Feed 1: 1345.2 g deionized water, 64.7 g emulsifier 1, 72.8 g emulsifier 6, 24.3 g acrylic acid, 48.5 g acrylamide (50 wt% aqueous solution), 1261.0 g butyl acrylate, and 1115.5 g methyl methacrylate. Feed 2: 69.3 g sodium persulfate aqueous solution (7 wt%). The reaction mixture was post-polymerized at 85°C for 30 min. Then feed 3 and feed 4 were added over 60 min. Feed 3: 24.3 g of tert-butyl hydroperoxide aqueous solution (10 wt%). Feed 4: 21.8 g of sulfinate aqueous solution (10 wt%). The reaction mixture was then cooled to ambient temperature and neutralized to pH 8-9 using sodium hydroxide aqueous solution. Tg (dried dispersion): 20℃ Average particle size (DLS): 127 nm Solids content: 47.9 wt% 5. Application properties of polymer latex 5.1 Water absorption

[0254] The polymer latex was diluted to 25 wt%. The latex was then poured onto a rubber sheet (6.7 x 14.9 cm) to obtain a transparent film with a thickness of approximately 750 µm after drying. This film was placed on a frame with gauze and kept for 7 days to allow it to dry completely. Two films (2 x 2 cm) were then cut and weighed. The films were then individually stored in 100 ml glass bottles of deionized water for 24 hours (w dry). They were then removed from the deionized water, wiped to remove all adhering water droplets, and weighed again (w moist). The water absorption rate was calculated using the following formula and given as a percentage by weight:

[0255] The results are summarized in Table 6.

[0256] 5.2 Elongation at break was measured according to DIN 53504 for the elasticity of polymer latex (examples C1, C2, C3, and D1 to D6) films or paint films. Free films with a dry film thickness of approximately 500 µm were prepared and dried at room temperature for 28 days. Each sample was then cut into five S2-bone shapes and the actual film thickness was measured. Elongation measurements were performed at a fixed stretching rate of 200 mm min⁻¹ at room temperature to obtain the elongation at break (expressed as elongation %) and the maximum tensile strength (expressed as N mm⁻²) relative to the initial sample length. Both values ​​were reported as the average of the five measurements.

[0257] The results are summarized in Table 6.

[0258] 5.3 Formulation of the Compound Examples C5 and D15 to D22 polymer latexes were tested using the following transparent coating formulations. For this purpose, each polymer latex was conditioned to a solids content of 45% by weight by adding water, and then formulated into a letdown by mixing the latex with deionized water, a film preservative (Acticide MKN 9, Thor GmbH), and a degassing agent (Tego Airex 902W, Evonik). The individual amounts are given in Table 5.

[0259] The paste was prepared by weighing the individual components given in Table 5 into a polyethylene beaker and homogenizing it using a dynamic mixer (SpeedmixerTMDAC 600.1 FVZ, from Hauschild GmbH & Co.) according to the following schedule: 800 rpm for 1 min, 1000 rpm for 1 min, 1250 rpm for 2 min, and 1600 rpm for 2.3 min. This paste was then divided into different portions and added to previously prepared different paint mixtures, and then homogenized using a dynamic mixer according to the following schedule: 800 rpm for 1 min, 1000 rpm for 1 min, 1250 rpm for 1 min, and 1600 rpm for 1.3 min. Table 5 Quantity [g] Active content [wt%] product paste Deionized water 50.0 0 Defoamer 4.0 100 Tego Foamex 810 coalescing agent 25.0 100 Butyl diethylene glycol UV-A absorber 5.0 100 Tinuvin 1130 wetting agent 1.0 100 Surfinol AD ​​01 In-can preservatives 2.0 7.5 Acticide MBS Neutralizing agent 2.0 25 ammonia solution Medium shear thickener 12.0 45 Rheovis PU 1291 High shear thickener 20.0 20 Rheovis PU 1340 Paint mixing materials polymer latex 715.5 45 Deionized water 148.5 0 membrane preservatives 10.0 40 Acticide MKN 9 Degassing agent 3.0 100 Tego Aerex 902W

[0260] 5.4 Whitening / Bubble Formation Conditioning / Cleaning of Glass Plates according to ISO 1522: A 100-micron wet film of the coating formulations or polymer latexes (examples C1, C2, C3 and D1 to D6 and D15 to D22) described in Section 5.3 was poured onto the cleaned glass using an Erichsen Rakel applicator and dried for 1 day at RT (23°C) and RH (50%). A black background below the glass plate provides contrast. A large drop of deionized water (approximately 3 cm in diameter) was placed on the coating and the meter was turned on. Photographs and notes were provided after different exposure times (where 0 = anhydrous whitening and 5 = opaque white). Results are summarized in Tables 6 and 7.

[0261] In the same experiment, bubbling was evaluated and graded on a scale of 0 to 2. 0 means no visible bubbles, 1 means few small bubbles, and 2 means many large bubbles. The results are summarized in Table 7.

[0262] 5.5 Pendulum impact hardness was determined as described in ISO 1522. For this purpose, a 100-micron wet film of the coating formulation described in Section 5.3 was poured onto cleaned glass using an Erichsen Rakel and allowed to dry for a specified time. The pendulum impact hardness was then measured. The results are summarized in Table 8 below.

[0263] 5.6 Anti-adhesion was evaluated as follows. Six pine wood samples were arranged parallel, side-by-side, and directly contacting each other. The wood samples were cut in the same manner (tangential cut) with the growth rings oriented in the same direction. A 300 µm wet layer of the coating formulation described in Section 5.3 was applied to the middle region of the board using a coating applicator. For the anti-adhesion test, only four coated intermediate samples were used.

[0264] The coating was dried at 23°C / 50% relative humidity for 24 h. Two boards were stacked with the coated areas facing each other. The same procedure was performed using a second set of boards. A 5 kg weight (200 g / cm²) was placed on the contact surface (50 × 50 mm), and the boards were stored in an air-conditioned room (RH=50%) at 23°C. After 24 h, the weight was removed and the boards were manually separated.

[0265] The anti-adhesion property is evaluated according to the following levels based on the force and degree of damage to the manual separation plate: 0 = no adhesion (adhesion), separation is possible without force; 1 = slight adhesion; 2 = minor adhesion; 3 = moderate adhesion; 4 = strong adhesion; 5 = extremely strong adhesion, manual separation of the plate is impossible.

[0266] The results are summarized in Table 8.

[0267] 5.7 Durability to UV Radiation Exposure The durability of the coating to UV radiation exposure was evaluated according to EN927-6. For this purpose, pine boards were coated with the coating formulation described in Section 5.3. Otherwise, the test procedure was the same as EN927-6. The boards were removed after approximately 500 h intervals, and gloss measurements were performed at a 60° angle according to DIN 53778. The gloss retention rate is reported here as a percentage of the initial value. The results are summarized in Table 9. Table 6 polymer latex Water absorption rate [wt%] Elongation at break % Albinism 1) C1 5.6 268 2 D1 4.2 344 0 D2 4.4 407 0 C2 13.5 354 5 D3 8.4 413 4 D4 9.0 nd 3-4 C3 7.8 344 2 D5 6.0 407 2 D6 5.3 411 1 1) Evaluation after 240 min, using polymer latex as is on Table 7. polymer latex Albinism Bubbling 0 min 30 min 60 min 180 min 0 min 30 min 60 min 180 min C5 0 4 5 5 0 2 2 2 D15 0 3 4 5 0 0 0 1 D16 0 2 3.25 5 0 0 0 1 D17 0 3 4 5 0 0 0 1 D18 0 3 4.5 5 0 0 0 1 D19 0 2.5 3.75 5 0 0 0 1 D20 0 3 5 5 0 0 0 1 D21 0 3.5 5 5 0 0 2 2 D22 0 2.5 3.5 5 0 0 0 0 Table 8 Polymer latex Impact hardness [s] -1 ] Anti-adhesion 1 d 7 d 28 days viscous seal C5 19.6 28.0 29.4 1 0 D15 16.8 23.8 23.8 1 0 D16 16.8 25.2 26.6 2 0 D17 18.2 25.2 25.2 1 0 D18 18.2 26.6 28.0 1.5 0 D19 18.2 25.2 26.6 0.5 0 D20 18.2 25.2 26.6 1 0 D21 19.6 25.2 nd 0.25 0 D22 14.0 15.4 nd 1 0 Table 9 Polymer latex Gloss retention rate [%) 504 h 1008 h 1512 h 2016 h C5 91 90 92 88 D15 71 76 71 74 D16 88 88 85 85 D17 97 98 93 92 D18 91 89 91 91 D19 93 89 84 85 D20 100 100 100 100 D21 97 91 nd nd D22 91 75 nd nd

[0268] 5.8 The formulations were tested for polymer latexes of Examples C6 and D23 in the form of the following high-PVC formulation (PVC = 77%).

[0269] The paste was prepared by weighing the individual components given in Table 10 into a polyethylene beaker and homogenizing it at 1600 rpm for 5 min using a dynamic mixer (SpeedmixerTMDAC 600.1 FVZ, from Hauschild GmbH & Co.). After aging for 24 h, the paste was homogenized again at 1600 rpm for 15 min. Subsequently, the individual polymer emulsions and a variable amount of deionized water were added to the paste to achieve a total solids content of 62.8 wt.% in the paint and homogenized at 200 rpm for 3 min. Table 10: Quantity [g] Active content [wt%] product paste Deionized water 270.0 0 Thickener 4.0 100 Tylose MH 30000 YP4 Neutralizing agent 2.0 10 Sodium hydroxide Pigment dispersants 5.0 10 Calgon Ng Pigment dispersants 3.5 100 Dispex AA 4145 Defoamer 2.0 100 Foamstar ED 2523 pigment 80.0 100 Kronos 2044 filler 35.0 100 Speswhite porcelain clay (Porcelain Clay B) filler 235.0 100 Omyacarb 2 GU filler 205.0 100 Omyacarb 5 GU Paint mixing materials polymer latex 145.0 50 Deionized water 13.0 0

[0270] 5.8 Wet Abrasion / Opacity Opacity (or hiding power) reflects the ability of a coating to cover a substrate. It can be quantified by measuring the diffusion rate. Such measurements are performed by applying wet films of different thicknesses (e.g., 150, 200, 220, and 250 micrometers) to a specified control paper (e.g., a Leneta foil with black and white areas) using a scraper (i.e., a medical scraper) and then measuring the contrast ratio. The values ​​are then interpolated to produce the so-called diffusion rate, which is the reciprocal of the volume of paint per area required to cover the substrate at a given contrast ratio [m² / L] (the reciprocal of the film thickness). According to ISO DIN 13300, this given contrast ratio is, for example, 99.5% (for Class I opacifiers) or 98% (for Class II opacifiers).

[0271] The wet rub resistance (WSR) of the prepared latex paint was tested according to ISO 11998 using the non-woven pad method. WSR was evaluated based on the weight loss per unit area caused by abrasion, and the average thickness loss (given in µm) was calculated. Table 11: polymer latex WSR [µm] Diffusion rate at 98% [m² / L] Diffusion rate at 99.5% [m² / L] C6 29 6.7 4.5 D23 twenty two 7.4 4.9

[0272] The data in Table 11 show that, compared with the latex of Comparative Example C6, the latex of Example D23 provides better wet rub resistance and increased diffusion rate, thereby providing better opacity to the water-based coating composition.

[0273] 5.9 In semi-gloss paints containing polymer latex D24 and C7 respectively, the following components are used: Ingredients / Functions Product Name source Titanium dioxide pigment Kronos 4311 Kronos Worldwide, Inc contain 2-Amino-2-methyl-1-propanol neutralizer AMP-95 Angus Chemical Company Ammonium salts of hydrophobic copolymers as dispersants Tamol 165 A Dow Hyperbranched polymer defoamer Foamstar 2420 BASF SE Non-volatile, nonionic surfactants are used as surface homogenizers and wetting agents. Hydropalat WE 3320 BASF SE Nonionic associative thickeners Aquaflow® NHS-310 Ashland Polymer pigments Ropaque Ultra E Dow Filler derived from nepheline syenite Minex 10 Sibelco Cohesive 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate Texanol Eastman Low-odor coalescing agent Optifilm 400 Eastman biocides Proxel AQ Lonza fungicides Polyphase 663 Troy Corporation Nonionic associative thickeners Rheolate CVS 10 Elementis Nonionic associative thickeners Acrysol RM 895 Dow Green slope stony clay Attagel 50 BASF SE

[0274] a) Mix 315 g of Kronos 4311 pigment with 15 g of water using a semi-gloss latex D24 mixture. At low stirring speed, add 1.75 g of AMP-95 neutralizer (Angus Chemical Company), 5 g of propylene glycol (Univar), 2 g of Foamstar 2420 defoamer (BASF), 9 g of Tamol 165 A dispersant (Dow), and 3 g of Hydropalat WE 3320 wetting agent (BASF). At high stirring speed, add 1.5 g of Attagel 50 (BASF), 25 g of Minex 10 (Sibelco) filler, and 20 g of Aquaflow NHS-310 (Ashland) nonionic associative thickener and mix for 30 min. Subsequently, add 81 g of deionized water and filter the mixture through a 400 µm filter. Then add 524.77 g of binder from Example 1, 25 g of Ropaque Ultra E polymeric pigment (Dow), 2 g of Foamstar 2420 defoamer (BASF), 9 g of Texanol coalescing agent (Eastman), and 7.7 g of Optifilm 400 coalescing agent (Eastman) and mix for 5 min. Then add 2 g of Proxel AQ biocide (Lonza), 3 g of Polyphase 663 fungicide (Troy Corporation), and 3.7 g of Rheolate CVS 10 nonionic associative thickener (Elementis) and mix for 5 min. Finally, add 1.7 g of Acrysol RM 895 nonionic associative thickener (Dow) and stir the mixture at medium speed for 30 min.

[0275] b) Mix 315 g of Kronos 4311 pigment with 15 g of water using a semi-gloss latex C7 mixture. At low stirring speed, add 1.75 g of AMP-95 neutralizer (Angus Chemical Company), 5 g of propylene glycol (Univar), 2 g of Foamstar 2420 defoamer (BASF), 9 g of Tamol 165 A dispersant (Dow), and 3 g of Hydropalat WE 3320 wetting agent (BASF). At high stirring speed, add 1.5 g of Attagel 50 (BASF), 25 g of Minex 10 (Sibelco) filler, and 20 g of Aquaflow NHS-310 (Ashland) nonionic associative thickener and mix for 30 min. Subsequently, add 104 g of deionized water and filter the mixture through a 400 µm filter. Then add 505.05 g of binder from Example 2, 25 g of Ropaque Ultra E polymeric pigment (Dow), 2 g of Foamstar 2420 defoamer (BASF), 9 g of Texanol coalescing agent (Eastman), and 7.5 g of Optifilm 400 coalescing agent (Eastman) and mix for 5 min. Then add 2 g of Proxel AQ biocide (Lonza), 3 g of Polyphase 663 fungicide (Troy Corporation), and 4.5 g of Rheolate CVS 10 nonionic associative thickener (Elementis) and mix for 5 min. Finally, add 2 g of Acrysol RM 895 nonionic associative thickener (Dow) and stir the mixture at medium speed for 30 min.

[0276] 5.10 Application properties of semi-gloss paints containing polymer latexes of Example 24 and Comparative Example C7: Low shear viscosity was measured at 20°C 7 days after preparation of the semi-gloss paint according to ASTM D562. The results are summarized in Table 12.

[0277] The high shear viscosity was measured 7 days after the semi-gloss paint was prepared at 20°C according to ASTM D4287. The results are summarized in Table 12.

[0278] Opacity: Coating films were prepared using a 3-mil scraper on Leneta 3B black and white seal impression cards. The films were dried at room temperature for 24 hours. Opacity was determined spectrophotometrically as the ratio of the amount of light reflected from the dried coating on the black and white portions of the Leneta card. Opacity indicates the coating's ability to cover black surfaces. The results are summarized in Table 12.

[0279] Gloss: A semi-gloss coating film was prepared by applying a 3-mil scraper to Leneta 3B black and white seal impression cards. The film was dried at room temperature for 24 hours. The gloss was measured using a gloss meter at angles of 20°, 65°, and 80°. The results are summarized in Table 12.

[0280] The scrub resistance of semi-gloss paints containing polymer latex D24 or C7 was determined according to ASTM D2486. The scrub cycle was determined before failure occurred. The results are summarized in Table 12.

[0281] In the Quick-UV test conducted according to ASTM D4587, cycle 4, 1000 h, the yellowness index was determined according to ASTM E313. The results are summarized in Table 12. Table 12 Paint containing latex D24 Paint containing latex C7 Low shear viscosity, 7d [KU] 93.3 92.6 High shear viscosity, 7d [poise] 0.66 0.60 Opacity 97.8 97.5 20° gloss 14.0 11.3 65° gloss 50.4 47.5 80° gloss 83.7 79.3 Scrub resistance (pre-failure period) 1069 985 Yellowness index (ASTM E313) 0.85 0.82

[0282] Adhesion of intermediate coatings to aluminum was determined according to ASTM D3359. The results for semi-gloss paints containing polymer latex D24 were comparable to those containing polymer latex C7.

[0283] According to ASTM D4828, the detergency of semi-gloss paint containing polymer latex D24 is comparable to that containing polymer latex C7 for pencils, lipsticks, crayons, ballpoint pens, red wine, ketchup, coffee, and mustard (visual inspection).

[0284] Dust Absorption: Wipe the glaze on the yellow pine surface with water and let it dry overnight. Depending on the number of test specimens, divide the substrate into multiple sections. Apply the test paint specimens using a suitable brush at the natural diffusion rate. Allow the paint to cure at room temperature for 4 hours and 24 hours respectively. Then, cover half of the coated area with 2 inches of dry dust (Arizona or Carpet soil). Allow the board to stand for 15 minutes, then tilt it vertically and tap it to release the dust. Gently brush the dirty areas of each specimen (15 times).

[0285] The dust retained on the board coated with a semi-gloss paint containing polymer latex D24 is slightly less than that on the board coated with a semi-gloss paint containing polymer latex C7 (visual assessment).

Claims

1. An aqueous polymer latex of a film-forming copolymer obtainable by aqueous emulsion polymerization of an olefinic unsaturated monomer M, wherein the monomer M comprises, based on the total amount of monomer M, at least one monomer M1, from 20% to 90% by weight, selected from isobutyl acrylate, 2-methylbutyl acrylate, and isoamyl acrylate, and mixtures thereof; and at least one monomer M2, based on the total amount of monomer M, from 0% to 55% by weight, selected from ethyl acrylate, n-propyl acrylate, n-butyl acrylate, n-amyl acrylate, C6-C20-alkyl acrylate, and C5-C20-alkyl methacrylate, and mixtures thereof; Based on the total amount of monomer M, at least one monomer M3, ranging from 5% to 50% by weight, is selected from tert-butyl acrylate, C1-C4-alkyl methacrylate, C5-C20-cycloalkyl acrylate, C5-C20-cycloalkyl methacrylate, C5-C20-cycloalkyl methacrylate, C5-C20-cycloalkyl methyl methacrylate, C5-C20-cycloalkyl methyl methacrylate, wherein the cycloalkyl group in the above monomers is mono-, bis-, or tricyclic and wherein one or two non-adjacent CH2 moieties of the cycloalkyl group may be replaced by oxygen atoms, and wherein the cycloalkyl group may be unsubstituted or carry 1, 2, 3, or 4 methyl groups; and monovinyl aromatic monomers and mixtures thereof; based on the total amount of monomer M, at least one monomer M4, ranging from 0.05% to 4% by weight, is selected from monoolefinic unsaturated monomers having acidic groups; The total amount of monomers M1 and M2, based on the total amount of olefinic unsaturated monomer M, ranges from 45% to 94.95% by weight, and the total amount of monomers M1, M2 and M3, based on the total amount of olefinic unsaturated monomer M, is at least 90% by weight.

2. The aqueous polymer latex of claim 1, wherein the monomer M1 is isobutyl acrylate.

3. The aqueous polymer latex of claim 1, wherein the monomer M1 is isoamyl acrylate or a mixture comprising isoamyl acrylate and 2-methyl butyl acrylate in an amount of at least 80% based on the total amount of monomer M1.

4. The aqueous polymer latex of any one of claims 1 to 3, wherein at least the carbon atoms of the isobutyl, 2-methylbutyl and isopentyl groups in the monomer M1 are of biological origin.

5. The aqueous polymer latex of any one of claims 1 to 3, wherein the monomer M2 is selected from the group consisting of n-butyl acrylate and 2-ethylhexyl acrylate and mixtures thereof.

6. The aqueous polymer latex of any one of claims 1 to 3, wherein the monomer M3 comprises methyl methacrylate.

7. The aqueous polymer latex of claim 6, wherein the monomer M3 is selected from methyl methacrylate and a combination of methyl methacrylate and at least one other monomer M3 selected from tert-butyl acrylate, n-butyl methacrylate, cyclohexyl methacrylate, isocamphenyl methacrylate and styrene.

8. The aqueous polymer latex of any one of claims 1 to 3, wherein the monomer M4 is selected from acrylic acid, methacrylic acid, itaconic acid, and combinations thereof.

9. The aqueous polymer latex of any one of claims 1 to 3, wherein the monomer M further comprises at least one monoolefinic unsaturated, nonionic monomer M5, wherein the monomer M5 has a solubility of at least 60 g / L in deionized water at 20°C and 1 bar.

10. The aqueous polymer latex of claim 9, wherein the monomer M5 is selected from the group consisting of nonionic monoolefin unsaturated monomers having functional groups selected from the group consisting of hydroxyalkyl, primary carboxylamine, urea, and ketone groups, and combinations thereof.

11. The aqueous polymer latex of any one of claims 1 to 3, wherein the monomers M consist of: i. 25% to 90% by weight of isobutyl acrylate as monomer M1, based on the total amount of monomer M; ii. 0% to 50% by weight of at least one monomer M2, selected from ethyl acrylate, n-propyl acrylate, n-butyl acrylate, C5-C20-alkyl acrylate, and C5-C20-alkyl methacrylate, based on the total amount of monomer M; iii. Based on the total amount of monomer M, at least one monomer M3, ranging from 10% to 45% by weight, selected from tert-butyl acrylate, C1-C4-alkyl methacrylate, C5-C20-cycloalkyl acrylate, C5-C20-cycloalkyl methacrylate, C5-C20-cycloalkyl methacrylate, C5-C20-cycloalkyl methyl methacrylate, C5-C20-cycloalkyl methyl methacrylate, wherein the cycloalkyl group in the above monomers is mono-, bis-, or tricyclic and one or two non-adjacent CH2 moieties of the cycloalkyl group may be replaced by oxygen atoms, and wherein the cycloalkyl group may be unsubstituted or carry one, two, three, or four methyl groups; and monovinyl aromatic monomers; iv. Based on the total amount of monomer M, one or more monoolefinic unsaturated monomers M4, ranging from 0.05% to 4% by weight; v. Based on the total weight of monomer M, one or more nonionic monomers M5, ranging from 0% to 9.95% by weight.

12. An aqueous polymer latex as claimed in any of claims 1 to 3, wherein the monomer M comprises or is composed of the following: i. 50% to 70% by weight of isobutyl acrylate as monomer M1 based on the total amount of monomer M; iii. Based on the total amount of monomer M, 30% to 50% by weight of methyl methacrylate is used as monomer M3; iv. Based on the total amount of monomer M, 0.1% to 4% by weight of monoalkenyl unsaturated carboxylic acid is used as monomer M4; v. Based on the total amount of monomer M, 0% to 5% by weight of monoolefinic unsaturated carboxylic acid amides are used as monomer M5a; vi. Based on the total weight of monomer M, 0% to 10% by weight of one or more olefinic unsaturated nonionic monomers different from those monomers M1, M3, M4 and M5a.

13. An aqueous polymer latex as claimed in any one of claims 1 to 3, wherein, as determined by quasi-elastic light scattering, the copolymer particles contained in the polymer latex have a Z-average particle size in the range of 30 nm to 500 nm, and specifically in the range of 40 nm to 350 nm.

14. An aqueous polymer latex as claimed in any one of claims 1 to 3, wherein the polymer particles comprise a polymer phase with a glass transition temperature (Tg) in the range of -25°C to +40°C.

15. An aqueous polymer latex as claimed in any one of claims 1 to 3, wherein the polymer particles comprise a polymer phase (1) having a glass transition temperature (Tg) (1) in the range of -25°C to +40°C and another polymer phase (2) having a glass transition temperature (Tg) (2) in the range of +50°C to +150°C.

16. The aqueous polymer latex of claim 15, wherein at least 75% by weight of monomer M1 is present in the polymer phase (1) based on the total amount of monomer M1 present in the monomers M.

17. A method for producing an aqueous polymeric latex as claimed in any one of claims 1 to 16, comprising performing aqueous emulsion polymerization on monomer M.

18. The method of claim 17, wherein the aqueous emulsion polymerization is carried out by a monomer feeding method, wherein at least 90% of the monomers M to be polymerized are supplied to the polymerization vessel in the form of an aqueous emulsion of monomers.

19. Use of an aqueous polymeric latex as claimed in any one of claims 1 to 16, as a binder in a water-based coating composition.

20. A water-based coating composition comprising c) a binder polymer in the form of an aqueous polymer latex as claimed in any one of claims 1 to 16; and d) at least one other component that is generally used in water-based coating compositions and is not a binder.

21. The water-based coating composition of claim 20, which is a latex paint, a latex paint specifically used in architectural coatings, wood coatings or wood staining compositions, or a latex paint used in interior coatings.

22. The water-based coating composition of any one of claims 20 or 21, comprising titanium dioxide pigment.

23. The water-based coating composition of claim 22, wherein the polymer of the polymer latex is in the range of 0.1:5.0 to 5.0:0.1 by weight.

24. Use of a waterborne polymer latex as claimed in any one of claims 1 to 16, for improving the resistance of a coating obtained from a water-based coating composition to water or moisture, or for improving the flexibility of a coating obtained from a water-based coating composition.