Waterborne polymer latex suitable as binder for copolymers in waterborne coating compositions

Abstract

Therefore, the present invention relates to aqueous polymer latexes of copolymers obtainable by aqueous emulsion polymerization of olefinically unsaturated monomers M, wherein the olefinically unsaturated monomers M comprise i. 5% to 90%, particularly 10% to 70%, especially 10% to 50% by weight of monomer M, which is 1-hexyl acrylate; ii. 0% to 70% by weight of at least one monomer M2, selected from C2-C5-alkyl esters of acrylic acid other than tert-butyl acrylate, and C7-C4-alkyl esters of acrylic acid. 20 C5-C of alkyl esters and methacrylic acid 20 iii. alkyl esters and mixtures thereof; iii. at least one monomer M3, selected from tert-butyl acrylate, C1-C4-alkyl esters of methacrylic acid, and C5-C4-alkyl esters of acrylic acid, based on 5% to 70% by weight of the total amount of monomer M. 20 -Cycloalkyl esters, C5-C of methacrylic acid 20 -Cycloalkyl esters, C5-C of acrylic acid 20 -Cycloalkyl methyl esters, C5-C of methacrylic acid 20 The invention relates to cycloalkyl methyl esters, wherein the cycloalkyl group in the monomers is monocyclic, bicyclic, or tricyclic, and wherein one or two non-adjacent CH2 moieties of the cycloalkyl group can be replaced by oxygen atoms, and wherein the cycloalkyl group can be unsubstituted or have one, two, three, or four methyl groups, as well as monovinyl aromatic monomers, methylene-γ-butyrolactone, and mixtures thereof; wherein the total amount of monomers M1 and M2 is in the range of 10% to 90% by weight based on the total amount of olefinically unsaturated monomer M, and wherein the total amount of monomers M1, M2, and M3 is at least 90% by weight based on the total amount of olefinically unsaturated monomer M. The invention also relates to a method for producing the aqueous polymer latex of the invention. The invention further relates to the use of these polymer latexes as adhesives in aqueous coating compositions and aqueous adhesive compositions, particularly as adhesives in aqueous coating compositions.

Description

[0001] This invention relates to aqueous polymer latexes of copolymers obtainable by aqueous emulsion polymerization of olefinically unsaturated monomers M, wherein these olefinically unsaturated monomers M comprise combinations of (meth)acrylates as monomers. The invention also relates to a method for producing such polymer latexes and to the use of these polymer latexes as binders in aqueous coating compositions. Furthermore, the invention relates to an aqueous coating composition containing a binder polymer in the form of an aqueous polymer latex as defined herein and at least one additional component that is conventionally used in aqueous coating compositions and is not a binder.

[0002] Polymer latex, also known as polymer dispersion, is commonly known, particularly, as a binder or binder component for use in coating compositions, also referred to as a co-binder. As a binder or co-binder in a coating composition, polymer latex should in particular provide good coating properties, such as high hardness, good adhesion, good opacity, good wet scrub resistance, good detergency, and low dust accumulation and low water absorption.

[0003] 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. In particular, it is difficult to simultaneously reconcile different coating property requirements using binders. Often, attempts to improve one property of the coating by varying the polymer composition of the binder result in a significant deterioration of other properties of the coating.

[0004] While the polymer dispersions described in this art have particular advantages in one or more respects, they do not always possess a well-balanced set of characteristics. Furthermore, they are based solely on monomers prepared from fossil sources. Given the ongoing discussions regarding the impact of CO2 emissions, there is a need to reduce fossil carbon in polymer latexes. The term bio-based means that the monomers are prepared at least partially from renewable raw materials such as plants, plant parts, plant waste, biomass, etc. These products are referred to as bio-based and are characterized by traceability. 14 C carbon content. It is also possible to convert these materials into suitable feedstocks, such as bio-naphtha, as described, for example, in EP 2 290 045 A1 or EP 2 290 034 A1. Such feedstocks typically enter chemical production systems, such as steam crackers, where they are converted along the chemical value chain into products such as acrylic acid, methacrylic acid, acrylates, methacrylates, etc. The renewable material content of these products is determined by mass balance and can be allocated to these products.

[0005] WO 2014 / 207389 describes the use of 2-octyl acrylate from renewable resources in the production of polymer latex. This polymer latex is proposed as an adhesive.

[0006] WO 2022 / 018013 describes polymer latexes based on acrylate monomers, methacrylate monomers, and / or monovinyl aromatic monomers, containing a certain amount of monomers selected from isobutyl acrylate and isoamyl acrylate and mixtures thereof. Coating compositions prepared therefrom produce coatings with improved coating properties such as resistance to whitening, water absorption, and flexibility. Isobutyl acrylate and isoamyl acrylate can be obtained—at least in terms of their alkanoic fraction—from biological sources, and thus allow for a reduction in fossil carbon in the polymer latex.

[0007] However, there is still a need to provide polymer latexes that are at least partially based on bio-based monomers and have acceptable or improved application characteristics that make them suitable as binders in waterborne coating compositions, particularly for external and internal application.

[0008] Surprisingly, it was found that polymer latexes based on a combination of a certain amount of 1-hexyl acrylate (monomer M1 hereinafter) with other conventional or bio-based monomers M2 and M3 as defined herein improved the coating properties of the coating composition, particularly hardness and coating rate (opacity). Furthermore, 1-hexyl acrylate can be obtained from biological sources—at least in terms of its alkanoic portion—and thus allows for a reduction in fossil carbon in the polymer latex.

[0009] Therefore, the present invention relates to aqueous polymer latexes of copolymers obtainable by aqueous emulsion polymerization of olefinically unsaturated monomers M, wherein these olefinically unsaturated monomers M contain...

[0010] i. Based on 5% to 90% by weight of monomer M, particularly 10% to 70% by weight, especially 10% to 50% by weight of monomer M1, which is 1-hexyl acrylate;

[0011] ii. At least one monomer M2, comprising 0% to 70% by weight of monomer M, selected from C2-C5-alkyl esters of acrylic acid other than tert-butyl acrylate, and C7-C4-alkyl esters of acrylic acid. 20 -C5-C of alkyl esters and methacrylic acid 20 -Alkyl esters and mixtures thereof;

[0012] iii. At least one monomer M3, comprising 5% to 70% by weight of monomer M, selected from tert-butyl acrylate, C1-C4-alkyl esters of methacrylate, and C5-C4-alkyl esters of acrylic acid. 20 -Cycloalkyl esters, C5-C of methacrylic acid20 -Cycloalkyl esters, C5-C of acrylic acid 20 -Cycloalkyl methyl esters, C5-C of methacrylic acid 20 -Cycloalkyl methyl esters, wherein the cycloalkyl group in the monomer is monocyclic, bicyclic or tricyclic, and wherein one or two non-adjacent CH2 moieties of the cycloalkyl group can be replaced by oxygen atoms, and wherein the cycloalkyl group can be unsubstituted or have one, two, three or four methyl groups, as well as monovinyl aromatic monomers, methylene-γ-butyrolactone and mixtures thereof.

[0013] iv. At least one monomer M4, selected from mono-olefinic unsaturated monomers having acidic groups, wherein the amount of monomer M4 is particularly in the range of 0.05% to 5% by weight based on the total weight of the olefinic unsaturated monomer M;

[0014] The total amount of monomers M1 and M2 is in the range of 10% to 90% by weight of the total amount of olefin-based unsaturated monomer M, and the total amount of monomers M1, M2 and M3 is at least 90% by weight of the total amount of olefin-based unsaturated monomer M.

[0015] The present invention also relates to a method for producing the aqueous polymer latex of the present invention. The method includes performing an aqueous emulsion polymerization of monomer M.

[0016] The present invention also relates to the use of these polymer latexes as adhesives in waterborne coating compositions and waterborne adhesive compositions, particularly as adhesives in waterborne coating compositions.

[0017] Furthermore, this invention relates to water-based coating compositions containing...

[0018] a) Adhesive polymers in the form of aqueous polymer latex as defined herein; and

[0019] b) At least one additional component that is conventionally used in water-based coating compositions and is not a binder.

[0020] This invention relates to several benefits.

[0021] - Polymer latex is stable and provides a good and well-balanced set of application characteristics for waterborne coating compositions, such as improved hardness, low dust accumulation, good scrub resistance and improved opacity.

[0022] Because polymer latex contains a significant amount of monomers M1, M2, and / or M3, at least some of monomer M1, as well as some of monomers M2 and M3, which are available from biorenewable sources, they allow for a significant reduction in the need for fossil carbon, particularly by at least 10%, especially at least 25%, or even at least 40%, and up to 100%. The incorporation of biocarbon and the reduction of fossil carbon can reduce the carbon footprint of polymer latex.

[0023] Due to their well-balanced application characteristics, polymer latexes are particularly suitable as binders in waterborne architectural coatings and have beneficial properties in waterborne primers and waterborne topcoat formulations, as well as exterior and interior architectural paints.

[0024] 1-Hexyl acrylate is an ester of 1-hexanol and acrylic acid, and can be described by the following chemical formula:

[0025]

[0026] Its carbon atoms, especially the carbon atoms in the n-hexyl group of 1-hexyl acrylate, can be bio-based.

[0027] Throughout this specification, the term "bio-based" means that the corresponding compound is at least partially derived from molecules obtained from biological renewable resources such as biomass. Such molecules are characterized by a bio-carbon content of at least 90 mol-%, preferably at least 95 mol-%, for example 100 mol-%, based on the total amount of carbon atoms in the corresponding molecule such as 1-hexanol, isobutanol, or 2-octanol.

[0028] The term "biocarbon" indicates that the carbon is of biological origin and comes from biomaterials / renewable resources. Herein and below, renewable source and biorenewable source are used synonymously and refer to sources other than fossil sources. Biocarbon content and biomaterial content are expressions indicating the same value. Renewable source materials or biomaterials are organic materials in which carbon originates from CO2 recently (on a human scale) fixed from the atmosphere through photosynthesis. Biomaterials (100% naturally derived carbon) have a carbon content greater than 10... -12 Typically about 1.2 × 10 -12 isotope ratio 14 C / 12 C, while the isotopic ratio of fossil materials 14 C / 12 C is zero. In fact, isotopes 14 C is formed in the atmosphere and then integrated via photosynthesis over timescales of up to several decades. 14 The half-life of carbon is 5,730 years. Therefore, materials derived from photosynthesis, i.e., typical plants, must possess isotopes. 14The maximum content of C. 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).

[0029] Throughout this specification and throughout the entire specification, the term "(meth)acryloyl" includes both acryloyl and methacryloyl. Therefore, the term "(meth)acrylate" includes acrylate and methacrylate, and the term "(meth)acrylamide" includes acrylamide and methacrylamide.

[0030] Herein and throughout this specification, the terms "waterborne coating composition" and "waterborne adhesive composition" respectively mean a liquid waterborne coating or adhesive composition containing an amount of water sufficient to achieve flowability as a continuous phase.

[0031] The terms “wt.-%” and “by weight % (% bw)” are used synonymously here and throughout the specification.

[0032] In this and throughout the specification, the term “pphm” means the number of parts per 100 monomers, i.e., the number of weight parts per 100 monomers, and corresponds to the relative amount of a substance as a percentage by weight based on the total amount of monomer M.

[0033] Throughout this specification and in all its contents, the term "olefinically unsaturated monomer" should be understood as a monomer having at least one C=C double bond, such as 1, 2, 3, or 4 C=C double bonds, which are free radical polymerizable, i.e., polymerizable under the conditions of an aqueous free radical emulsion polymerization method to obtain a polymer with a carbon atom backbone. Throughout this specification and in all its contents, the term "monoolefinically 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 method.

[0034] Throughout this specification, the terms "ethoxylation" and "polyethoxylation" are used synonymously and refer to compounds having oligomeric or polyoxyethylene groups formed by repeating units O-CH2CH2. In this context, the term "degree of ethoxylation" refers to the average number of repeating units O-CH2CH2 in these compounds.

[0035] In this and throughout the specification, in the context of compounds, and especially monomers, the term "nonionic" means that the corresponding compound does not have any ionic functional group or any functional group that can be converted into an ionic group by protonation or deprotonation.

[0036] The prefix C used herein and throughout this specification in conjunction with the compound or molecular part n -C mEach indicates the range of possible carbon atoms that a molecular moiety or compound can have. The term "C1-C" n "alkyl" refers to a group consisting of a straight-chain or branched saturated hydrocarbon group having 1 to n carbon atoms. The term "C"... n / C m "Alkyl" indicates a mixture of two alkyl groups, one with n carbon atoms and the other with m carbon atoms.

[0037] For example, the term C1-C 20 Alkyl groups refer to straight-chain or branched saturated hydrocarbon groups having 1 to 20 carbon atoms, while the terms C1-C4 alkyl refer to straight-chain or branched saturated hydrocarbon groups having 1 to 4 carbon atoms, and C5-C6 alkyl refer to alkyl groups having 1 to 20 carbon atoms. 20 Alkyl groups refer to straight-chain or branched saturated hydrocarbon groups having 5 to 20 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylpropyl (isopropyl), 1,1-dimethylethyl (tert-butyl), pentyl, 1-methylbutyl, 2-methylbutyl, 3-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, Heptadecanyl, Octadecanyl, Nonadecanyl, Eicosyl, Dodecyl, Dodecyl, Isotridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Octadecanyl, Nonadecanyl, Eicosyl, Dodecyl, Dodecyl, and Dodecyl, and their isomers, especially mixtures of isomers, such as "Isononyl" and "Isodecyl". Examples of C1-C4-alkyl groups are, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, or 1,1-dimethylethyl.

[0038] As used in this article, the term "C5-C" 20 "-cycloalkyl" refers to an unsubstituted monocyclic, bicyclic, or tricyclic alicyclic group, or one substituted with 1, 2, 3, or 4 methyl groups, wherein the C5-C6 group is a cycloalkyl group. 20 -The total number of carbon atoms in cycloalkyl groups is 5 to 20. (C5-C)20 Examples of cycloalkyl groups include, but are not limited to, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclohexadecyl, norbornyl (= bicyclo[2.2.1]heptyl) and isobornyl (= 1,7,7-trimethylbicyclo[2.2.1]heptyl). In cycloalkyl groups, one or two CH2 groups may be replaced by non-adjacent oxygen ring atoms to produce heterocyclic aliphatic groups. Examples of such groups include, but are not limited to, oxopentyl-2-yl, oxopentyl-3-yl, oxan-2-yl, oxan-3-yl, oxan-4-yl, 1,3-dioxopentyl-2-yl, 1,3-dioxopentyl-4-yl, 2,2-dimethyl-1,3-dioxopentyl-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.

[0039] As used in this article, the term "C5-C" 20 "-cycloalkylmethyl" refers to C5-C as defined in this article. 20 -Cycloalkyl groups, which are bonded via methylene groups.

[0040] As used herein, the term "isobornyl" (= 1,7,7-trimethylbicyclo[2.2.1]heptyl) refers to a monocyclic alicyclic group having 10 carbon atoms that is either unsubstituted or substituted with 1, 2, 3 or 4 methyl groups.

[0041] According to the present invention, monomer M comprises monomer M1, wherein monomer M1 is 1-hexyl acrylate.

[0042] 1-Hexyl acrylate is typically produced by esterification of acrylic acid with 1-hexanol or by transesterification of methyl acrylate or ethyl acrylate with 1-hexanol. 1-Hexyl acrylate is available from biological sources, at least in terms of its alkanol fraction, and thus allows for the reduction of fossil carbon in polymer latexes.

[0043] 1-Hexanol can be obtained, for example, as a byproduct of the catalytic Guerbet-type conversion of (bio)ethanol to butanol, which is then preferably produced by fermentation of biomass, typically derived from crops containing sugars or starches, as described, for example, in Y. Xie et al., J. Am. Chem. Soc. 2016, 138, 29, 9077-9080; H. Aitchison et al., ACS Catalysis. 2016, 6, 10, 7125-7132; and US 2010 / 0298613 A1. 1-Hexanol prepared in this manner has a biocarbon content of about 100 mol-%, and thus allows for the production of 1-hexyl acrylate with a biocarbon content of at least 67 mol-%.

[0044] Acrylic acid used for esterification can be obtained from fossil sources according to standard procedures. Alternatively, acrylic acid can also be prepared from renewable raw materials, such as those specified in WO 2006 / 092272, DE 10 2006 039 203 A, or EP 2 922 580.

[0045] Preferably, at least a portion of the precipitate used to synthesize monomer M1 is derived from biorenewable raw materials. Therefore, specific embodiments of the invention relate to polymer latexes as defined herein, wherein at least the carbon atoms of the 1-hexyl group in monomer M1 are of biological origin, i.e., they are at least partially composed of biocarbon. Specifically, the 1-hexanol used to produce monomer M1 preferably has a biocarbon content of at least 90 mol-% based on the total carbon atoms in 1-hexanol. This content is advantageously higher, particularly 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 produced from renewable materials. However, to date, acrylic acid and / or methacrylic acid produced from biomaterials are not readily available on a large scale. Therefore, monomer M1 preferably has a biocarbon content of at least 60 mol-%, particularly at least 66.5 mol-%, based on the total carbon atoms in 1-hexyl acrylate. By using monomer M1 that is at least partially of biological origin, the need for fossil carbon in polymer latexes can be significantly reduced. In particular, it is possible to achieve at least 10 mol-%, especially at least 15 mol-%, or at least 20 mol-%, or higher, such as at least 30 mol-%, at least 40 mol-%, at least 50 mol-%, or at least 60 mol-%, or higher amounts of bio-derived carbon.

[0046] The total amount of monomer M1 is based on the total weight of monomer M, ranging from 5% to 90% by weight, particularly from 7.5% to 70% by weight, or from 10% to 55% by weight, particularly from 12% to 50% by weight.

[0047] In addition to monomer M1, the monomer M of the polymer forming the latex may contain one or more monomers M2 as defined above.

[0048] The appropriate monomer M2 is selected from the following groups:

[0049] - C2-C5-alkyl esters of acrylic acid other than tert-butyl acrylate, including but not limited to ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, 2-methylbutyl acrylate and isopentyl acrylate (= 3-methylbutyl acrylate).

[0050] - Acrylic C7-C 20 alkyl esters, including but not limited to n-heptyl acrylate, n-octyl acrylate, 2-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, isodecyl acrylate, 2-propylheptyl acrylate, lauryl acrylate, and C-acrylate. 12 / C 14 -Alkyl ester, C-acrylate 12 -C 15 -Alkyl ester, isotridecyl acrylate, C-acrylate 17 -Alkyl ester, C-acrylate 16 / C 18 -Alkyl esters and stearyl acrylate;

[0051] -C5-C of methacrylic acid 20 -Alkyl esters, 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, C-methacrylate 12 / C 14 -Alkyl ester, C-methacrylic acid 12 -C 15 -Alkyl ester, isotridecyl methacrylate, C-methacrylate 16 / C 18 -Alkyl esters and stearyl methacrylate; and

[0052] - Its mixture.

[0053] Preferred monomer M2 is selected from the group consisting of: ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, 2-methylbutyl acrylate, isoamyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-octyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate, and mixtures thereof. Preferably, monomer M2 is selected from the group consisting of: n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, and 2-octyl acrylate, and mixtures thereof. Isoamyl acrylate, 2-methylbutyl acrylate, isobutyl acrylate, n-heptyl acrylate, and / or 2-octyl acrylate may be produced from fossil sources or may be at least partially bio-based. Specifically, the carbon atoms of the isopentyl, 2-methylbutyl, isobutyl, n-heptyl, and / or 2-octyl groups in isoamyl acrylate, 2-methylbutyl acrylate, isobutyl acrylate, n-heptyl acrylate, and 2-octyl acrylate are biologically derived, meaning the monomers are obtained by esterification of acrylic acid (which may be bio-based or fossil-derived) with bio-based isoamyl alcohol, 2-methylbutanol, isobutanol, 1-heptanol, or 2-octanol, respectively. In particular, the isobutyl group in isobutyl acrylate and / or the 2-octyl group in 2-octyl acrylate are biologically derived, meaning the monomers are obtained by esterification of acrylic acid (which may be bio-based or fossil-derived) with bio-based isobutanol or 2-octyl alcohol, respectively.

[0054] In the preferred embodiment group M2-A, monomer M2 comprises isobutyl acrylate, especially bio-based isobutyl acrylate. Specifically, monomer M2 is isobutyl acrylate, especially bio-based isobutyl acrylate. In this preferred embodiment group, monomer M2 may also be isobutyl acrylate combined with at least one other acrylate C2-C5 or C7-C variety different from isobutyl acrylate. 10 Alkyl esters, such as especially n-butyl acrylate, isoamyl acrylate, 2-methylbutyl acrylate, n-heptyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate, and especially mixtures of n-butyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate.

[0055] In the context of this set of embodiments, it is preferred that the amount of isobutyl acrylate is in the range of 1% to 70%, particularly 10% to 60%, particularly 20% to 50% by weight based on the total amount of monomer M.

[0056] In another preferred embodiment group M2-B, monomer M2 comprises n-butyl acrylate, and in particular n-butyl acrylate. In this embodiment group, n-butyl acrylate may be the sole monomer or n-butyl acrylate combined with at least one other acrylate C2-C5 or C7-C variety different from n-butyl acrylate. 10Alkyl esters, such as, in particular, isobutyl acrylate, isoamyl acrylate, 2-methylbutyl acrylate, n-heptyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate, and especially mixtures of isobutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate.

[0057] In the context of this set of embodiments, it is preferred that the amount of n-butyl acrylate is in the range of 1% to 60%, particularly 10% to 50%, particularly 15% to 40% by weight based on the total amount of monomer M.

[0058] Isobutyl acrylate, 2-methylbutyl acrylate, isoamyl acrylate, n-heptyl acrylate, and 2-octyl acrylate are typically produced by esterification of acrylic acid with isobutanol (2-methylprop-1-ol), 2-methylbutanol, isoamyl alcohol (3-methylbut-1-ol), 1-heptanol, or 2-octanol, respectively, or by transesterification of methyl acrylate or ethyl acrylate with isobutanol (2-methylprop-1-ol), 2-methylbut-1-ol, isoamyl alcohol (3-methylbut-1-ol), or 2-octanol, respectively.

[0059] Isobutanol, 2-methylbutanol, and isoamyl alcohol, and mixtures thereof, can be produced on a large scale by fermentation from various renewable feedstocks (including corn, wheat, sorghum, barley, and sugarcane), particularly from cellulose-containing raw materials and therefore from biological or renewable sources. In particular, fermentation can produce a mixture containing different alkanols, from which isobutanol, 2-methylbut-1-ol, and 3-methylbut-1-ol can be separated using conventional techniques such as fractionation. Thus, pure alcohols (purity > 90%) can be obtained, or mixtures containing at least 80%, particularly at least 90%, of at least two alcohols selected from the group consisting of isobutanol, 2-methylbut-1-ol, and 3-methylbut-1-ol. For example, a mixture containing at least 80% by weight of 2-methylbutanol and 3-methylbutanol and up to 20% by weight of isobutanol can be used for esterification or transesterification. In this mixture, the molar ratio of 3-methylbutanol to 2-methylbut-1-ol can vary, for example, from 1:10 to 10:1, and particularly within the range of 1:1 to 10:1. 1-Heptanol can be produced via the catalytic hydrogenation of heptanal, which is prepared by the pyrolysis of ricinoleic acid, obtainable from castor oil (i.e., a biomass source). 2-Octanol can be produced via the base-catalyzed thermal cracking of ricinoleic acid, with sebacic acid as a byproduct. Castor oil, primarily composed of ricinoleic acid, is the main feedstock. Therefore, incorporating these monomers M2 into the polymer latex significantly increases the amount of biochar in the polymer latex. The incorporation of biochar and the reduction of fossil carbon can reduce the carbon footprint of the polymer latex.

[0060] Therefore, specific embodiments of the invention relate to polymer latexes as defined herein, wherein at least the carbon atoms of isobutyl, 2-methylbutyl, isopentyl, n-heptyl, and 2-octyl groups, respectively, in monomer M2, particularly at least the carbon atoms of the isobutyl group, are of biological origin, i.e., they are at least partially composed of biocarbon. Specifically, the isobutanol, 2-methylbut-1-ol, 3-methylbutanol, 1-heptanol, and 2-octanol used to produce monomer M2 preferably have a biocarbon content of at least 90 mol-% based on the total amount of carbon atoms in isobutanol, 2-methylpentanol, 3-methylbutanol, 1-heptanol, and 2-octanol, respectively. This content is advantageously higher, particularly 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 produced from renewable materials. However, to date, acrylic acid produced from biomaterials is not readily available on a large scale. Therefore, monomer M2 preferably has a bio-carbon content of at least 51 mol-%, particularly at least 54 mol-%, and especially at least 57 mol-%, based on the total amount of carbon atoms in isobutyl acrylate, 2-methylbutyl acrylate, isoamyl acrylate, n-heptyl acrylate, and 2-octyl acrylate, respectively. By using monomer M2, which is at least partially of biological origin, the demand for fossil carbon in polymer latex can be significantly reduced. In particular, it is possible to achieve an amount of at least 5 mol-%, particularly at least 10 mol-%, or at least 15 mol-%, or higher, such as 20 mol-%, or 30 mol-%, or higher of bio-derived carbon.

[0061] The total amount of monomer M2 is based on the total weight of monomer M, ranging from 0% to 70% by weight, particularly from 0% to 60% by weight, or from 1% to 60% by weight, particularly from 1% to 50% by weight, or from 5% to 50% by weight.

[0062] In the specific embodiment group M2-1, based on the total amount of monomer M, monomer M comprises:

[0063] - 15% to 80% by weight, preferably 20% to 70% by weight, and especially 25% to 60% by weight of monomer M1;

[0064] - Monomer M2, comprising 0% to less than 5% by weight, preferably 0% to 3% by weight, and particularly 0% by weight; and

[0065] -Based on monomer M, which comprises 20% to 70%, preferably 30% to 70% by weight and particularly 40% to 65% by weight, monomer M3, which contains methyl methacrylate or methyl methacrylate.

[0066] In another specific embodiment group M2-2, based on the total amount of monomer M, monomer M comprises:

[0067] - 5% to 50% by weight, preferably 5% to 30% by weight, and especially 5% to 20% by weight of monomer M1;

[0068] - 5% to 70% by weight, preferably 15% to 60% by weight, and particularly 20% to 50% by weight, of monomer M2 as defined in the above example group M2-A, wherein monomer M2 is particularly selected from isobutyl acrylate and mixtures of isobutyl acrylate with at least one of n-butyl acrylate, 2-octyl acrylate, and 2-ethylhexyl acrylate, wherein the carbon atoms of isobutyl acrylate and 2-octyl acrylate (if present) are preferably at least partially of biological origin; and

[0069] - 10% to 70% by weight, preferably 20% to 65% by weight, and particularly 30% to 62% by weight, of monomer M3, which contains methyl methacrylate or methyl methacrylate.

[0070] In other specific embodiment groups M2-3, based on the total amount of monomer M, monomer M comprises:

[0071] - 5% to 50% by weight, preferably 5% to 30% by weight, and especially 5% to 20% by weight of monomer M1;

[0072] - 5% to 70% by weight, preferably 15% to 60% by weight, and particularly 20% to 50% by weight, of monomer M2 as defined in the above example group M2-B, wherein monomer M2 is particularly selected from n-butyl acrylate and mixtures thereof with at least one of isobutyl acrylate, 2-octyl acrylate, and 2-ethylhexyl acrylate, wherein the carbon atoms of isobutyl acrylate and 2-octyl acrylate (if present) are preferably at least partially of biological origin; and

[0073] - 10% to 70% by weight, preferably 20% to 65% by weight, and particularly 30% to 62% by weight, of monomer M3, which contains methyl methacrylate or methyl methacrylate.

[0074] Here, examples M2-1 and M2-2 are particularly preferred, and especially example M2-1.

[0075] In addition to monomers M1 and M2, the monomer M of the polymer forming the latex may contain one or more monomers M3 as defined above.

[0076] Suitable monomer M3 can be selected from the following groups:

[0077] - C1-C4-alkyl esters of methacrylate, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, isobutyl methacrylate and tert-butyl methacrylate.

[0078] - tert-butyl acrylate;

[0079] -C5-C of (meth)acrylic acid 20 -Cycloalkyl esters, including but not limited to cyclopentyl acrylate, cyclopentyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, norbornyl acrylate, norbornyl methacrylate, isobornyl acrylate, isobornyl 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;

[0080] -C5-C of (meth)acrylic acid 20 -Cycloalkyl methyl esters, including but not limited to cyclopentyl methacrylate, cyclopentyl methyl methacrylate, cyclohexyl methyl acrylate, cyclohexyl methyl methacrylate, 1,3-dioxolane-4-yl methyl acrylate, 1,3-dioxolane-4-yl methyl methacrylate, 2,2-dimethyl-1,3-dioxolane-4-yl methyl acrylate, 2,2-dimethyl-1,3-dioxolane-4-yl methyl methacrylate, oxypentyl-2-yl methyl acrylate (tetrahydrofurfuryl acrylate), and oxypentyl-2-yl methyl methacrylate (tetrahydrofurfuryl methacrylate).

[0081] -Methylene-γ-butyrolactone, such as α-methylene-γ-butyrolactone or γ-methylene-γ-butyrolactone;

[0082] - Monovinyl aromatic monomers, such as styrene, 2-methylstyrene, or 4-methylstyrene; and

[0083] - Its mixture.

[0084] In the preferred group of embodiments, monomer M3 is selected from the group consisting of:

[0085] - C1-C4-alkyl esters of methacrylate, particularly methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and tert-butyl methacrylate;

[0086] - tert-butyl acrylate;

[0087] - Cyclopentyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, isobornyl methacrylate;

[0088] -α-methylene-γ-butyrolactone;

[0089] -Styrene; and

[0090] - Its mixture.

[0091] In this group, monomer M3 is specifically selected from the following groups:

[0092] -Methyl methacrylate, n-butyl methacrylate;

[0093] - tert-butyl acrylate;

[0094] - Cyclopentyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate;

[0095] -α-methylene-γ-butyrolactone;

[0096] -Styrene; and

[0097] - Its mixture.

[0098] In a specific group of embodiments, monomer M3 comprises methyl methacrylate in an amount of at least 50%, particularly at least 80%, or 100% by weight of the total amount of monomer M3 in monomer M. More particularly, monomer M3 is selected from the group consisting of methyl methacrylate and combinations of methyl methacrylate with at least one additional monomer M3 selected from n-butyl methacrylate, tert-butyl acrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, α-methylene-γ-butyrolactone, and styrene, particularly selected from n-butyl methacrylate, tert-butyl acrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, and styrene.

[0099] In this specific set of embodiments, the preferred monomer M3 is methyl methacrylate.

[0100] The total amount of monomer M3 is based on the total weight of monomer M, ranging from 5% to 70% by weight, particularly from 15% to 70% by weight or from 25% to 65% by weight, particularly from 35% to 62% by weight.

[0101] The total amount of monomers M1 and M2 is preferably in the range of 10% to 90% by weight of the total amount of olefin-based unsaturated monomer M, particularly in the range of 20% to 80% by weight, and particularly in the range of 25% to 70% by weight.

[0102] The total amount of monomers M1, M2 and M3 is based on the total amount of olefinic unsaturated monomer M being at least 90% by weight, particularly at least 94% by weight, and especially at least 97% by weight.

[0103] The weight ratio of M1 to M3 is typically in the range of 1:10 to 5:1, particularly in the range of 1:6 to 3:1, preferably in the range of 1:5 to 2:1, and especially in the range of 1:4 to 1.5:1.

[0104] If M2 is present, the weight ratio of M1 to M2 is typically in the range of 1:10 to 2:1, particularly 1:4 to 1.5:1, and preferably in the range of 1:3 to 1:1.

[0105] These monomers M further comprise at least one monomer M4, which is selected from monoolefinic unsaturated monomers having acidic groups.

[0106] Suitable monomers M4 include, but are not limited to,

[0107] - Mono-olefinic 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;

[0108] - Mono-olefinic unsaturated dicarboxylic acids with 4 to 6 carbon atoms, such as itaconic acid, citraconic acid and fumaric acid;

[0109] - Half esters of mono-olefinic unsaturated dicarboxylic acids with 4 to 6 carbon atoms and C1-C4 alkanols such as methanol or ethanol, such as itaconic acid, citraconic acid, maleic acid or fumaric acid and methanol or ethanol.

[0110] - Mono-olefinic unsaturated sulfonic acids, such as vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, and 2-acrylamido-2-methylpropane sulfonic acid.

[0111] - Monoene-bonded unsaturated phosphonic acids, such as vinylphosphonic acid, allylphosphonic acid, styrenephosphonic acid, and 2-acrylamido-2-methylpropanephosphonic acid.

[0112] - Monoalkyl unsaturated phosphoric acid, such as monophosphates of hydroxyalkyl acrylates, monophosphates of hydroxyalkyl methacrylates, monophosphates of alkoxylated hydroxyalkyl acrylates and monophosphates of alkoxylated hydroxyalkyl methacrylates, especially monophosphates of hydroxyethyl acrylate, hydroxypropyl acrylate or hydroxybutyl acrylate, monophosphates of hydroxyethyl methacrylate, hydroxypropyl methacrylate or hydroxybutyl methacrylate, 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.

[0113] The aforementioned monomer M4 can exist in its acidic form or in its salt form, particularly in its alkali metal salt or ammonium salt form.

[0114] Among the monomers M4 described above, preferred are mono-alkenyl unsaturated monocarboxylic acids, mono-alkenyl unsaturated dicarboxylic acids, and mono-alkenyl unsaturated sulfonic acids and their salts, particularly alkali metal salts and ammonium salts. Particularly preferred are acrylic acid, methacrylic acid, itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid and their salts, particularly alkali metal salts and ammonium salts, and combinations thereof. More preferred are mono-alkenyl unsaturated monocarboxylic acids and mono-alkenyl unsaturated dicarboxylic acids and their salts, particularly alkali metal salts and ammonium salts, especially acrylic acid, methacrylic acid, itaconic acid, their salts, particularly alkali metal salts and ammonium salts, and combinations thereof. In a specific group of examples, monomer M4 comprises acrylic acid or its salts, particularly alkali metal salts or ammonium salts. In particular, monomer M4 is acrylic acid or its salts, particularly alkali metal salts or ammonium salts, or a mixture of acrylic acid and methacrylic acid or its salts, particularly alkali metal salts or ammonium salts. In another specific group of examples, monomer M4 comprises methacrylic acid or its salts, particularly alkali metal salts or ammonium salts. In particular, monomer M4 is methacrylic acid or its salt, especially an alkali metal salt or an ammonium salt.

[0115] The total amount of monomer M4 is specifically based on the total weight of monomer M, ranging from 0.05% to 5% by weight or from 0.1% to 4% by weight, particularly from 0.05% to 3.5% by weight or from 0.1% to 3% by weight, particularly from 0.2% to 2.5% by weight or from 0.5% to 2% by weight or from 0.5% to 1.5% by weight.

[0116] Monomer M may further comprise at least one mono-olefinically unsaturated nonionic monomer M5, which has a solubility of at least 60 g / L in deionized water at 20°C and 1 bar.

[0117] Suitable monomer M5 is selected from the group consisting of nonionic monoolefin unsaturated monomers having functional groups selected from the group consisting of: hydroxyalkyl, especially hydroxy-C2-C4-alkyl, primary formamide, urea, ketone and combinations thereof.

[0118] The total amount of monomer M5 will generally not exceed 10% by weight of the total amount of monomer M, particularly 7% by weight. Specifically, if present, the total amount of monomer M5 is generally 0% to 9.95% by weight, 0.05% to 9.95% by weight, particularly 0.1% to 7% by weight, particularly 0.1% to 5% by weight, or 0.1% to 4% by weight, or 0.5% to 3% by weight, or 1% to 3% by weight.

[0119] Examples of monomers M5 having a formamide group (hereinafter, monomer M5a) include, but are not limited to, primary amides of monoalkenyl unsaturated monocarboxylic acids having 3 to 6 carbon atoms, such as acrylamide and methacrylamide, and C1-C4-alkylamides of monoalkenyl unsaturated monocarboxylic acids having 3 to 6 carbon atoms, such as N-methacrylamide, N-ethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, N-butylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-isopropylmethacrylamide, and N-butylmethacrylamide. Most preferably, monomer M5a is selected from acrylamide and methacrylamide, and especially arylamides.

[0120] Examples of monomers M5 (hereinafter referred to as monomer M5b) having a urea group 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-oxoimidazoline group, such as 2-(2-oxo-imidazoline-1-yl)ethyl acrylate and 2-(2-oxo-imidazoline-1-yl)ethyl methacrylate (which are also referred to as 2-urea acrylate and methacrylic acid, respectively). Urea esters, N-(2-acryloyloxyethyl)urea, N-(2-methacryloyloxyethyl)urea, N-(2-(2-oxo-imidazolidine-1-yl)ethyl)acrylamide, N-(-2-(2-oxo-imidazolidine-1-yl)ethyl)methacrylamide, and allyl or vinyl-substituted ureas and allyl or vinyl-substituted 2-oxoimidazoline compounds, such as 1-allyl-2-oxoimidazoline, N-allylurea and N-vinylurea.

[0121] An example of a monomer M5 (hereinafter referred to as monomer M5c) having a ketone group is...

[0122] - C2-C8-oxoalkyl esters of acrylic acid or methacrylic acid and N-C2-C8-oxoalkylamides of acrylic acid or methacrylic acid, such as diacetone acrylamide (DAAM) and diacetone methacrylic acid, and

[0123] - 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 is 2-acetylacetoxy group (also known as acetoacetoxy group) having the formula OC(=O)-CH2-C(=O)-CH3, such as acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate and 2-(acetoacetoxy)ethyl methacrylate.

[0124] In the specific example group, monomer M5 comprises acrylamide or methylarylamide, and particularly comprises acrylamide. In particular, monomer M5 is acrylamide or methylarylamide, and particularly acrylamide.

[0125] Preferably, monomer M comprises or consists of the following items:

[0126] i. 1-Hexyl acrylate as monomer M1, based on a total amount of 5% to 90% by weight, particularly 7.5% to 70% by weight or 10% to 55% by weight, particularly 12% to 50% by weight;

[0127] ii. Based on the total amount of monomer M, 0% to 70% by weight, particularly 0% to 60% by weight, or 1% to 60% by weight, particularly 1% to 50% by weight, or 5% to 50% by weight, at least one monomer M2, which comprises isobutyl acrylate or isobutyl acrylate.

[0128] iii. Based on the total amount of monomer M, at least one monomer M3 comprising 5% to 70% by weight, particularly 15% to 70% by weight or 25% to 65% by weight, particularly 35% to 62% by weight, which contains methyl methacrylate or methyl methacrylate.

[0129] iv. One or more mono-olefinic unsaturated monomers M4, selected from mono-olefinic unsaturated monomers having acidic groups, based on a total amount of monomer M of 0.05% to 5% by weight, or 0.1% to 4% by weight, particularly 0.05% to 3.5% by weight, or 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;

[0130] v. If present, one or more nonionic monomers M5, comprising 0% to 9.95% by weight, 0.05% to 9.95% by weight, particularly 0.1% to 7% by weight, particularly 0.1% to 5% by weight, or 0.1% to 4% by weight, or 0.5% to 3% by weight, or 1% to 3% by weight, of the total weight of monomer M, having a solubility of at least 60 g / L in deionized water at 20°C and 1 bar.

[0131] or

[0132] i. 1-Hexyl acrylate as monomer M1, based on a total amount of 5% to 90% by weight, particularly 7.5% to 70% by weight or 10% to 55% by weight, particularly 12% to 50% by weight;

[0133] ii. Based on the total amount of monomer M, 0% to 70% by weight, particularly 0% to 60% by weight, or 1% to 60% by weight, particularly 1% to 50% by weight, or 5% to 50% by weight, at least one monomer M2, which comprises n-butyl acrylate or n-butyl acrylate.

[0134] iii. Based on the total amount of monomer M, at least one monomer M3 comprising 5% to 70% by weight, particularly 15% to 70% by weight or 25% to 65% by weight, particularly 35% to 62% by weight, which contains methyl methacrylate or methyl methacrylate.

[0135] iv. One or more mono-olefinic unsaturated monomers M4, selected from mono-olefinic unsaturated monomers having acidic groups, based on a total amount of monomer M of 0.05% to 5% by weight, or 0.1% to 4% by weight, particularly 0.05% to 3.5% by weight, or 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;

[0136] v. If present, one or more nonionic monomers M5, comprising 0% to 9.95% by weight, 0.05% to 9.95% by weight, particularly 0.1% to 7% by weight, particularly 0.1% to 5% by weight, or 0.1% to 4% by weight, or 0.5% to 3% by weight, or 1% to 3% by weight, of the total weight of monomer M, having a solubility of at least 60 g / L in deionized water at 20°C and 1 bar.

[0137] The total amount of monomers M1 and M3 is in the range of 10% to 98% by weight of the total amount of olefin-based unsaturated monomer M, particularly in the range of 22.5% to 85% by weight, particularly in the range of 35% to 70% by weight, and wherein the total amount of monomers M1, M2 and M3 is at least 90% by weight of the total amount of olefin-based unsaturated monomer M, particularly at least 94% by weight, particularly at least 97% by weight.

[0138] In group 1 of the specific embodiments, monomer M includes or consists of the following items:

[0139] i. 15% to 79.95% by weight, particularly 20% to 69.85% by weight, particularly 25% to 59.4% by weight, of 1-hexyl acrylate as monomer M1;

[0140] ii. Based on 20% to 70% by weight, particularly 30% to 70% by weight, especially 40% to 65% by weight, of monomer M3, which contains methyl methacrylate or methyl methacrylate;

[0141] iii. Based on the total amount of monomer M, 0.05% to 5% by weight, particularly 0.1% to 4% by weight, particularly 0.5% to 3% by weight, of one or more mono-olefinic unsaturated monomers M4, which are selected from mono-olefinic unsaturated monomers having acidic groups;

[0142] iv. One or more nonionic monomers M5, comprising 0% to 9.95% by weight, particularly 0.05% to 5% by weight, and especially 0.1% to 4% by weight, of monomer M, having a solubility of at least 60 g / L in deionized water at 20°C and 1 bar.

[0143] The total amount of monomers M1 and M3 is based on the total amount of olefinic unsaturated monomer M, which is at least 85% by weight, particularly at least 90% by weight, especially at least 95% by weight;

[0144] or

[0145] i. 5% to 50% by weight of monomer M, particularly 5% to 30% by weight, especially 5% to 20% by weight of 1-hexyl acrylate as monomer M1;

[0146] ii. Isobutyl acrylate as monomer M2, based on a total amount of 5% to 70% by weight, particularly 15% to 60% by weight, particularly 20% to 50% by weight;

[0147] iii. Based on 10% to 70% by weight, particularly 20% to 65% by weight, especially 30% to 62% by weight, of monomer M3, which contains methyl methacrylate or methyl methacrylate;

[0148] iv. Based on the total amount of monomer M, 0.05% to 5% by weight, particularly 0.1% to 4% by weight, particularly 0.5% to 3% by weight, of one or more mono-olefinic unsaturated monomers M4, selected from mono-olefinic unsaturated monomers having acidic groups;

[0149] v. One or more nonionic monomers M5, comprising 0% to 9.95% by weight, particularly 0.05% to 5% by weight, and especially 0.1% to 4% by weight, of monomer M, having a solubility of at least 60 g / L in deionized water at 20°C and 1 bar.

[0150] The total amount of monomers M1 and M3 is in the range of 15% to 90% by weight of the total amount of olefin-based unsaturated monomer M, particularly in the range of 25% to 80% by weight, particularly in the range of 35% to 70% by weight, and the total amount of monomers M1, M2 and M3 is at least 90% by weight of the total amount of olefin-based unsaturated monomer M, particularly at least 94% by weight, particularly at least 97% by weight;

[0151] or

[0152] i. 5% to 50% by weight of monomer M, particularly 5% to 30% by weight, especially 5% to 20% by weight of 1-hexyl acrylate as monomer M1;

[0153] ii. Based on a total amount of monomer M, 5% to 70% by weight, particularly 15% to 60% by weight, especially 20% to 50% by weight, monomer M2, which is a mixture of isobutyl acrylate and at least one of n-butyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate;

[0154] iii. Based on 10% to 70% by weight, particularly 20% to 65% by weight, especially 30% to 62% by weight, of monomer M3, which contains methyl methacrylate or methyl methacrylate;

[0155] iv. Based on the total amount of monomer M, 0.05% to 5% by weight, particularly 0.1% to 4% by weight, particularly 0.5% to 3% by weight, of one or more mono-olefinic unsaturated monomers M4, selected from mono-olefinic unsaturated monomers having acidic groups;

[0156] v. One or more nonionic monomers M5, comprising 0% to 9.95% by weight, particularly 0.05% to 5% by weight, and especially 0.1% to 4% by weight, of monomer M, having a solubility of at least 60 g / L in deionized water at 20°C and 1 bar.

[0157] The total amount of monomers M1 and M3 is in the range of 15% to 90% by weight of the total amount of olefin-based unsaturated monomer M, particularly in the range of 25% to 80% by weight, particularly in the range of 35% to 70% by weight, and the total amount of monomers M1, M2 and M3 is at least 90% by weight of the total amount of olefin-based unsaturated monomer M, particularly at least 94% by weight, particularly at least 97% by weight;

[0158] or

[0159] i. 5% to 50% by weight of monomer M, particularly 5% to 30% by weight, especially 5% to 20% by weight of 1-hexyl acrylate as monomer M1;

[0160] ii. Based on 5% to 70% by weight, particularly 15% to 60% by weight, especially 20% to 50% by weight of monomer M2, which is selected from n-butyl acrylate and combinations of n-butyl acrylate with at least one of isobutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate.

[0161] iii. Based on 10% to 70% by weight, particularly 20% to 65% by weight, especially 30% to 62% by weight, of monomer M3, which contains methyl methacrylate or methyl methacrylate;

[0162] iv. Based on the total amount of monomer M, 0.05% to 5% by weight, particularly 0.1% to 4% by weight, particularly 0.5% to 3% by weight, of one or more mono-olefinic unsaturated monomers M4, selected from mono-olefinic unsaturated monomers having acidic groups;

[0163] v. One or more nonionic monomers M5, comprising 0% to 9.95% by weight, particularly 0.05% to 5% by weight, and especially 0.1% to 4% by weight, of monomer M, having a solubility of at least 60 g / L in deionized water at 20°C and 1 bar.

[0164] The total amount of monomers M1 and M3 is in the range of 15% to 90% by weight of the total amount of olefin-based unsaturated monomer M, particularly in the range of 25% to 80% by weight, particularly in the range of 35% to 70% by weight, and wherein the total amount of monomers M1, M2 and M3 is at least 90% by weight of the total amount of olefin-based unsaturated monomer M, particularly at least 94% by weight, particularly at least 97% by weight.

[0165] In subgroup 1a of specific embodiment group 1, monomer M comprises or consists of the following items:

[0166] i. 1-Hexyl acrylate as monomer M1, comprising 15% to 79.95%, particularly 20% to 69.85%, particularly 25% to 59.4% by weight, of the total amount of monomer M, wherein at least the carbon atom of the 1-hexyl group in the 1-hexyl acrylate is of biological origin, particularly the biogenic carbon content of the 1-hexyl acrylate is at least 60 mol-%, particularly at least 66.5 mol-%.

[0167] ii. Based on 20% to 70% by weight, particularly 30% to 70% by weight, especially 40% to 65% by weight, of monomer M3, which contains methyl methacrylate or methyl methacrylate;

[0168] iii. Based on the total amount of monomer M, 0.05% to 5% by weight, particularly 0.1% to 4% by weight, particularly 0.5% to 3% by weight, of one or more mono-olefinic unsaturated monomers M4, which are selected from mono-olefinic unsaturated monomers having acidic groups;

[0169] iv. One or more nonionic monomers M5, comprising 0% to 9.95% by weight, particularly 0.05% to 5% by weight, and especially 0.1% to 4% by weight, of monomer M, having a solubility of at least 60 g / L in deionized water at 20°C and 1 bar.

[0170] The total amount of monomers M1 and M3 is based on the total amount of olefinic unsaturated monomer M, which is at least 85% by weight, particularly at least 90% by weight, especially at least 95% by weight;

[0171] or

[0172] i. 1-Hexyl acrylate, comprising 5% to 50% by weight, particularly 5% to 30% by weight, especially 5% to 20% by weight, of monomer M1, wherein at least the carbon atom of the 1-hexyl group in the 1-hexyl acrylate is of biological origin, particularly the biogenic carbon content of the 1-hexyl acrylate is at least 60 mol-%, particularly at least 66.5 mol-%.

[0173] ii. Isobutyl acrylate comprising 5% to 70%, particularly 15% to 60%, especially 20% to 50% by weight of monomer M2, of which at least the carbon atom of the isobutyl group in the isobutyl acrylate is of biological origin, particularly the biomass content of the isobutyl acrylate is at least 54 mol-%, particularly at least 57 mol-%.

[0174] iii. Based on 10% to 70% by weight, particularly 20% to 65% by weight, especially 30% to 62% by weight, of monomer M3, which contains methyl methacrylate or methyl methacrylate;

[0175] iv. Based on the total amount of monomer M, 0.05% to 5% by weight, particularly 0.1% to 4% by weight, particularly 0.5% to 3% by weight, of one or more mono-olefinic unsaturated monomers M4, selected from mono-olefinic unsaturated monomers having acidic groups;

[0176] v. One or more nonionic monomers M5, comprising 0% to 9.95% by weight, particularly 0.05% to 5% by weight, and especially 0.1% to 4% by weight, of monomer M, having a solubility of at least 60 g / L in deionized water at 20°C and 1 bar.

[0177] The total amount of monomers M1 and M3 is in the range of 15% to 90% by weight of the total amount of olefin-based unsaturated monomer M, particularly in the range of 25% to 80% by weight, particularly in the range of 35% to 70% by weight, and the total amount of monomers M1, M2 and M3 is at least 90% by weight of the total amount of olefin-based unsaturated monomer M, particularly at least 94% by weight, particularly at least 97% by weight;

[0178] or

[0179] i. 1-Hexyl acrylate, comprising 5% to 50% by weight, particularly 5% to 30% by weight, especially 5% to 20% by weight, of monomer M1, wherein at least the carbon atom of the 1-hexyl group in the 1-hexyl acrylate is of biological origin, particularly the biogenic carbon content of the 1-hexyl acrylate is at least 60 mol-%, particularly at least 66.5 mol-%.

[0180] ii. Based on 5% to 70% by weight, particularly 15% to 60% by weight, especially 20% to 50% by weight, of monomer M2, which is a mixture of isobutyl acrylate with at least one of n-butyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate, wherein at least the carbon atom of the isobutyl group in the isobutyl acrylate is of biological origin, particularly the biochar content of the isobutyl acrylate is at least 54 mol-%, particularly at least 57 mol-%.

[0181] iii. Based on 10% to 70% by weight, particularly 20% to 65% by weight, especially 30% to 62% by weight, of monomer M3, which contains methyl methacrylate or methyl methacrylate;

[0182] iv. Based on the total amount of monomer M, 0.05% to 5% by weight, particularly 0.1% to 4% by weight, particularly 0.5% to 3% by weight, of one or more mono-olefinic unsaturated monomers M4, selected from mono-olefinic unsaturated monomers having acidic groups;

[0183] v. One or more nonionic monomers M5, comprising 0% to 9.95% by weight, particularly 0.05% to 5% by weight, and especially 0.1% to 4% by weight, of monomer M, having a solubility of at least 60 g / L in deionized water at 20°C and 1 bar.

[0184] The total amount of monomers M1 and M3 is in the range of 15% to 90% by weight of the total amount of olefin-based unsaturated monomer M, particularly in the range of 25% to 80% by weight, particularly in the range of 35% to 70% by weight, and the total amount of monomers M1, M2 and M3 is at least 90% by weight of the total amount of olefin-based unsaturated monomer M, particularly at least 94% by weight, particularly at least 97% by weight;

[0185] or

[0186] i. 1-Hexyl acrylate, comprising 5% to 50% by weight, particularly 5% to 30% by weight, especially 5% to 20% by weight, of monomer M1, wherein at least the carbon atom of the 1-hexyl group in the 1-hexyl acrylate is of biological origin, particularly the biogenic carbon content of the 1-hexyl acrylate is at least 60 mol-%, particularly at least 66.5 mol-%.

[0187] ii. Based on 5% to 70% by weight, particularly 15% to 60% by weight, especially 20% to 50% by weight of monomer M2, which is selected from n-butyl acrylate and combinations of n-butyl acrylate with at least one of isobutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate.

[0188] iii. Based on 10% to 70% by weight, particularly 20% to 65% by weight, especially 30% to 62% by weight, of monomer M3, which contains methyl methacrylate or methyl methacrylate;

[0189] iv. Based on the total amount of monomer M, 0.05% to 5% by weight, particularly 0.1% to 4% by weight, particularly 0.5% to 3% by weight, of one or more mono-olefinic unsaturated monomers M4, selected from mono-olefinic unsaturated monomers having acidic groups;

[0190] v. One or more nonionic monomers M5, comprising 0% to 9.95% by weight, particularly 0.05% to 5% by weight, and especially 0.1% to 4% by weight, of monomer M, having a solubility of at least 60 g / L in deionized water at 20°C and 1 bar.

[0191] The total amount of monomers M1 and M3 is in the range of 15% to 90% by weight of the total amount of olefin-based unsaturated monomer M, particularly in the range of 25% to 80% by weight, particularly in the range of 35% to 70% by weight, and wherein the total amount of monomers M1, M2 and M3 is at least 90% by weight of the total amount of olefin-based unsaturated monomer M, particularly at least 94% by weight, particularly at least 97% by weight.

[0192] In addition to the monomers M1, M2, M3, M4, and M5 mentioned above, monomer M may contain one or more other monomers different from the monomers M described above. Suitable monomers M other than monomers M1, M2, M3, M4, and M5 include, but are not limited to, those mentioned above.

[0193] - Monomer M6, which is selected from monoolefinic unsaturated nonionic monomers having silane functional groups or epoxy groups;

[0194] - Monomer M7, which is selected from polyene unsaturated monomers, that is, monomers having at least two non-conjugated olefin unsaturated double bonds;

[0195] - Monomer M8, which is selected from monoolefinic unsaturated copolymerizable UV initiators.

[0196] Suitable monomers M6 include mono-olefinically unsaturated silane functional monomers (monomer M6a), such as monomers having at least one mono-, di-, and / or tri-C1-C4-alkoxysilane group in addition to an olefinically unsaturated double bond, such as vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxyethyltrimethoxysilane, methacryloxyethyltriethoxysilane, and mixtures thereof. Methacryloxypropyltrimethoxysilane and vinyltriethoxysilane are preferred. If present, the amount of silane functional monomer M6a will generally not exceed 1% by weight, and is often in the range of 0.01% to 1% by weight, preferably in the range of 0.05% to 0.7% by weight, based on the total amount of the olefinically unsaturated monomer M.

[0197] Suitable monomer M6 also includes mono-olefinic unsaturated monomers (monomer M6b) having at least one epoxy group, particularly glycidyl groups, such as glycidyl acrylate, glycidyl methacrylate, 2-glycidyloxyethyl acrylate, and 2-glycidyloxyethyl methacrylate. If present, the amount of monomer M6b will generally not exceed 2% by weight based on the total amount of olefinic unsaturated monomer M, and is often in the range of 0.01% to 2% by weight, preferably in the range of 0.05% to 1% by weight.

[0198] Monomer M may also contain a polyene-bonded unsaturated monomer (monomer M7), i.e., a monomer having at least two non-conjugated olefinic unsaturated double bonds. Based on the total amount of the olefinic unsaturated monomer M, the amount of monomer M7 will generally not exceed 1% by weight, and often falls within the range of 0% to 1% by weight, and especially 0% to 0.5% by weight.

[0199] Examples of polyene-bonded unsaturated monomers M7 include:

[0200] - Diesters of monoene-bonded unsaturated C3-C6 monocarboxylic acids with saturated aliphatic or alicyclic diols, especially diesters of acrylic acid or methacrylic acid, such as diacrylates and dimethacrylates of 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;

[0201] - Monoesters of monoene-bonded unsaturated C3-C6 monocarboxylic acids and monoene-bonded unsaturated aliphatic or alicyclic monohydroxy compounds, such as acrylates and methacrylates of vinyl alcohol, allyl alcohol, 2-propen-1-ol, 2-cyclohexen-1-ol, or norbornenol, such as allyl acrylate and allyl methacrylate; and

[0202] -Divinyl aromatic compounds, such as 1,3-divinylbenzene and 1,4-divinylbenzene.

[0203] The polymerized monoolefinically unsaturated copolymerizable UV initiator M8 induces crosslinking of the polymer chains upon exposure to sunlight. Monomer M8 contains olefinically unsaturated double bonds, particularly acrylate or methacrylate groups, and a portion that decomposes upon UV radiation, thereby forming free radicals. 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, DE3844444, EP 1213, and US 2015 / 0152297. Examples include, but are not limited to, 4-acryloyloxybenzophenone (= 4-benzoylphenyl acrylate), 4-methacryloyloxybenzophenone (= 4-benzoylphenyl 2-methacrylate), 4-(2-acryloyloxyethoxy)benzophenone (= 2-(4-benzoylphenoxy)ethyl acrylate), 4-(2-methacryloyloxyethoxy)benzophenone (= 2-(4-benzoylphenoxy)ethyl 2-methacrylate), O-(2-(meth)acryloyloxyethyl)-O-(benzoylphenyl) carbonate, and O-(2-(meth)acryloyloxyethyl)-O-(acetylphenyl) carbonate. Based on the total amount of the olefinically unsaturated monomer M, the amount of said monomer M8 will generally not exceed 1% by weight, and if present, is typically in the range of 0.01% to 1% by weight, particularly 0.02% to 0.5% by weight.

[0204] In specific embodiment group 2, monomer M consists of the following:

[0205] i. 1-Hexyl acrylate as monomer M1, comprising 15% to 79.95%, particularly 20% to 69.85%, particularly 25% to 59.4% by weight, of the total amount of monomer M, wherein at least the carbon atom of the 1-hexyl group in the 1-hexyl acrylate is of biological origin, particularly the biogenic carbon content of the 1-hexyl acrylate is at least 60 mol-%, particularly at least 66.5 mol-%.

[0206] ii. Based on 20% to 70% by weight, particularly 30% to 70% by weight, especially 40% to 65% by weight, of monomer M3, which contains methyl methacrylate or methyl methacrylate;

[0207] iii. Based on a total amount of monomer M, from 0.05% to 5% by weight, particularly from 0.1% to 4% by weight, particularly from 0.5% to 3% by weight, one or more monoolefinic unsaturated monomers M4 selected from acrylic acid, methacrylic acid, itaconic acid and combinations thereof;

[0208] iv. One or more nonionic monomers M5, comprising 0% to 9.95% by weight, particularly 0.05% to 5% by weight, especially 0.1% to 4% by weight, of monomer M, having a solubility of at least 60 g / L in deionized water at 20°C and 1 bar, having functional groups selected from the group consisting of hydroxyalkyl, primary formamide, urea, ketone, and combinations thereof; and

[0209] v. One or more monomers M7, based on the total weight of monomer M, at 0% to 1% by weight, and especially at 0% to 0.5% by weight;

[0210] The total amount of monomers M1 and M3 is based on the total amount of olefinic unsaturated monomer M, which is at least 85% by weight, particularly at least 90% by weight, especially at least 95% by weight;

[0211] or

[0212] i. 1-Hexyl acrylate, comprising 5% to 50% by weight, particularly 5% to 30% by weight, especially 5% to 20% by weight, of monomer M1, wherein at least the carbon atom of the 1-hexyl group in the 1-hexyl acrylate is of biological origin, particularly the biogenic carbon content of the 1-hexyl acrylate is at least 60 mol-%, particularly at least 66.5 mol-%.

[0213] ii. Isobutyl acrylate comprising 5% to 70%, particularly 15% to 60%, especially 20% to 50% by weight of monomer M2, of which at least the carbon atom of the isobutyl group in the isobutyl acrylate is of biological origin, particularly the biomass content of the isobutyl acrylate is at least 54 mol-%, particularly at least 57 mol-%.

[0214] iii. Based on 10% to 70% by weight, particularly 20% to 65% by weight, especially 30% to 62% by weight, of monomer M3, which contains methyl methacrylate or methyl methacrylate;

[0215] iv. Based on a total amount of monomer M, from 0.05% to 5% by weight, particularly from 0.1% to 4% by weight, particularly from 0.5% to 3% by weight, one or more mono-olefinic unsaturated monomers M4 selected from acrylic acid, methacrylic acid, itaconic acid and combinations thereof;

[0216] v. One or more nonionic monomers M5, comprising 0% to 9.95% by weight, particularly 0.05% to 5% by weight, particularly 0.1% to 4% by weight, of monomer M, having a solubility of at least 60 g / L in deionized water at 20°C and 1 bar, having functional groups selected from the group consisting of hydroxyalkyl, primary formamide, urea, ketone, and combinations thereof; and

[0217] vi. One or more monomers M7, comprising 0% to 1% by weight, particularly 0% to 0.5% by weight, of the total weight of monomer M;

[0218] The total amount of monomers M1 and M3 is in the range of 15% to 90% by weight of the total amount of olefin-based unsaturated monomer M, particularly in the range of 25% to 80% by weight, particularly in the range of 35% to 70% by weight, and the total amount of monomers M1, M2 and M3 is at least 90% by weight of the total amount of olefin-based unsaturated monomer M, particularly at least 94% by weight, particularly at least 97% by weight;

[0219] or

[0220] i. 1-Hexyl acrylate, comprising 5% to 50% by weight, particularly 5% to 30% by weight, especially 5% to 20% by weight, of monomer M1, wherein at least the carbon atom of the 1-hexyl group in the 1-hexyl acrylate is of biological origin, particularly the biogenic carbon content of the 1-hexyl acrylate is at least 60 mol-%, particularly at least 66.5 mol-%.

[0221] ii. Based on 5% to 70% by weight, particularly 15% to 60% by weight, especially 20% to 50% by weight, of monomer M2, which is a mixture of isobutyl acrylate with at least one of n-butyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate, wherein at least the carbon atom of the isobutyl group in the isobutyl acrylate is of biological origin, particularly the biochar content of the isobutyl acrylate is at least 54 mol-%, particularly at least 57 mol-%.

[0222] iii. Based on 10% to 70% by weight, particularly 20% to 65% by weight, especially 30% to 62% by weight, of monomer M3, which contains methyl methacrylate or methyl methacrylate;

[0223] iv. Based on a total amount of monomer M, from 0.05% to 5% by weight, particularly from 0.1% to 4% by weight, particularly from 0.5% to 3% by weight, one or more mono-olefinic unsaturated monomers M4 selected from acrylic acid, methacrylic acid, itaconic acid and combinations thereof;

[0224] v. One or more nonionic monomers M5, comprising 0% to 9.95% by weight, particularly 0.05% to 5% by weight, particularly 0.1% to 4% by weight, of monomer M, having a solubility of at least 60 g / L in deionized water at 20°C and 1 bar, having functional groups selected from the group consisting of hydroxyalkyl, primary formamide, urea, ketone, and combinations thereof; and

[0225] vi. One or more monomers M7, comprising 0% to 1% by weight, particularly 0% to 0.5% by weight, of the total weight of monomer M;

[0226] The total amount of monomers M1 and M3 is in the range of 15% to 90% by weight of the total amount of olefin-based unsaturated monomer M, particularly in the range of 25% to 80% by weight, particularly in the range of 35% to 70% by weight, and the total amount of monomers M1, M2 and M3 is at least 90% by weight of the total amount of olefin-based unsaturated monomer M, particularly at least 94% by weight, particularly at least 97% by weight;

[0227] or

[0228] i. 1-Hexyl acrylate, comprising 5% to 50% by weight, particularly 5% to 30% by weight, especially 5% to 20% by weight, of monomer M1, wherein at least the carbon atom of the 1-hexyl group in the 1-hexyl acrylate is of biological origin, particularly the biogenic carbon content of the 1-hexyl acrylate is at least 60 mol-%, particularly at least 66.5 mol-%.

[0229] ii. Based on 5% to 70% by weight, particularly 15% to 60% by weight, especially 20% to 50% by weight of monomer M2, which is selected from n-butyl acrylate and combinations of n-butyl acrylate with at least one of isobutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate.

[0230] iii. Based on 10% to 70% by weight, particularly 20% to 65% by weight, especially 30% to 62% by weight, of monomer M3, which contains methyl methacrylate or methyl methacrylate;

[0231] iv. Based on a total amount of monomer M, from 0.05% to 5% by weight, particularly from 0.1% to 4% by weight, particularly from 0.5% to 3% by weight, one or more mono-olefinic unsaturated monomers M4 selected from acrylic acid, methacrylic acid, itaconic acid and combinations thereof;

[0232] v. One or more nonionic monomers M5, comprising 0% to 9.95% by weight, particularly 0.05% to 5% by weight, particularly 0.1% to 4% by weight, of monomer M, having a solubility of at least 60 g / L in deionized water at 20°C and 1 bar, having functional groups selected from the group consisting of hydroxyalkyl, primary formamide, urea, ketone, and combinations thereof; and

[0233] vi. One or more monomers M7, comprising 0% to 1% by weight, particularly 0% to 0.5% by weight, of the total weight of monomer M;

[0234] The total amount of monomers M1 and M3 is in the range of 15% to 90% by weight of the total amount of olefin-based unsaturated monomer M, particularly in the range of 25% to 80% by weight, particularly in the range of 35% to 70% by weight, and wherein the total amount of monomers M1, M2 and M3 is at least 90% by weight of the total amount of olefin-based unsaturated monomer M, particularly at least 94% by weight, particularly at least 97% by weight.

[0235] Preferably, the copolymer particles contained in the polymer latex have a Z-mean particle size in the range of 30 to 500 nm, particularly in the range of 40 to 350 nm, as determined by quasi-elastic light scattering (QELS). The particle size distribution of the copolymer particles contained in the polymer latex can be unimodal or nearly 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 can also be multimodal or nearly multimodal, meaning that the particle size distribution function has at least two distinct maximum values ​​or at least one maximum value and at least one distinct shoulder.

[0236] Unless otherwise specified, 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. A high-performance particle size analyzer (HPPS) can be used. For this purpose, a sample of the aqueous polymer latex is diluted, and the dilution is analyzed. In the context of QELS, the aqueous dilution can have a polymer concentration ranging from 0.001% to 0.5% by weight, depending on the particle size. For most purposes, a suitable concentration would be 0.01% by weight. However, higher or lower concentrations can be used to achieve the optimal signal-to-noise ratio. Dilution can be achieved by adding the polymer latex to an aqueous solution of water or a surfactant to avoid flocculation. Typically, dilution is performed using a 0.1% by weight aqueous solution of a nonionic emulsifier (e.g., ethoxylated C16 / C18 alkanols with a degree of ethoxylation of 18) as the diluent. Measurement setup: HPPS from Malvern, automated, with continuous flow cuvettes and a Gilson autosampler. Parameters: Measurement temperature 20.0°C; measurement time 120 seconds (6 cycles, 20 s each); scattering angle 173°; laser wavelength 633 nm (HeNe); media refractive index 1.332 (aqueous); viscosity 0.9546 mPa·s. The measurements yielded the average values ​​(fitted averages) from the second-order cumulant analysis, i.e., the Z-means. The "fitted average" is the intensity-weighted average hydrodynamic particle size in nm.

[0237] Hydrodynamic particle size can also be determined by hydrodynamic chromatography (HDC), as described, for example, in H. Wiese's "Characterization of Aqueous Polymer Dispersions" in *Polymer Dispersions and Their Industrial Applications* (Wiley-VCH, 2002), pp. 41-73. For further details, refer to the following examples and descriptions.

[0238] In this specific set of examples, the copolymer particles contained in the polymer latex have a Z-mean particle size in the range of 30 to 200 nm, particularly in the range of 40 to 150 nm, as determined by QELS. In this specific set of examples, the particle size distribution of the copolymer particles contained in the polymer latex is particularly unimodal or nearly unimodal, meaning that the particle size distribution function has a single maximum value.

[0239] The copolymers contained in the polymer particles can form a single phase, or, if the polymer particles contain different copolymers, they can form different phases, which differ in terms of their monomer composition. Preferably, the polymer particles contained in the aqueous polymer latex of the present invention comprise a polymer phase having a glass transition temperature Tg of no more than 50°C and particularly at most 40°C, especially at most 30°C, preferably in the range of -40°C to +50°C, more preferably in the range of -25°C to +40°C and especially in the range of -20°C to +30°C.

[0240] The glass transition temperature mentioned herein is the actual glass transition temperature. The actual glass transition temperature can be experimentally determined by differential scanning calorimetry (DSC) according to ISO 11357-2:2013, preferably using sample preparation according to ISO 16805:2003.

[0241] The actual glass transition temperature depends on the monomer composition that forms the polymer, while the theoretical glass transition temperature can be calculated from the monomer composition used in emulsion polymerization. The theoretical glass transition temperature is typically calculated from the monomer composition using the Fox equation:

[0242] 1 / Tg t = x a / Tg a + x b / Tg b + .... x n / Tg n ,

[0243] In this equation, x a x b ....x n It is the mass fraction of monomers a, b, ... n and Tg a Tg b ....Tg nIt is the actual glass transition temperature (in Kelvin) of a homopolymer synthesized only from one of monomers 1, 2, ..., n in a single step. The Fox equation is described by TG Fox in Bull. Am. Phys. Soc [Bulletin of the American Physical Society]. 1956, 1, p. 123 and in Ullmann's Encyclopädie der technischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], Vol. 19, p. 18, 4th edition, VerlagChemie [Chemical Publishing House], Weinheim, 1980. The actual Tg values ​​of most homopolymers are known and are listed, for example, in Ullmann's Encyclopädie der technischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], 5th edition, Vol. A21, p. 169, Verlag Chemie [Chemical Publishing House], Weinheim, 1992. Other sources of glass transition temperatures for homopolymers are, for example, J. Brandrup, EH Immergut, Polymer Handbook, 1st edition, J. Wiley [John Wiley Publishing House], New York, 1966; 2nd edition, J. Wiley [John Wiley Publishing House], New York, 1975; 3rd edition, J. Wiley [John Wiley Publishing House], New York, 1989; and 4th edition, J. Wiley [John Wiley Publishing House], New York, 2004.

[0244] Typically, the theoretical glass transition temperature Tg is calculated using Fox as described in this paper. t The glass transition temperatures are similar to or even the same as those experimentally determined as described in this paper, and deviate from each other by no more than 5 K, and specifically by no more than 2 K. Therefore, appropriate monomers Ma, Mb…Mn and their mass fractions x in the monomer composition can be selected. a x b ....x n The actual and theoretical glass transition temperatures of polymer phases (1) and (2) are adjusted to achieve the desired glass transition temperatures Tg(1) and Tg(2), respectively. It is common sense for those skilled in the art to select appropriate amounts of monomers Ma, Mb…Mn to obtain copolymers and / or copolymer phases with the desired glass transition temperatures.

[0245] Typically, the copolymers formed by monomer M and contained in the polymer latex of the present invention are film-forming, meaning that the copolymer particles form a film during the drying of the polymer latex. Preferably, the aqueous copolymer latex of the present invention has a minimum film-forming temperature (MFT) of no more than 50°C and no more than 40°C. MFFT is defined as the lowest temperature at which a polymer latex applied to a substrate surface still forms a closed, uniform, and crack-free coating after drying (see Ullmann's Encyclopädie der technischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], Vol. 19, 4th edition, Verlag Chemie [Chemical Publishing House], Weinheim, 1980). The minimum film-forming temperature is related to the lowest glass transition temperature of the copolymer, but can typically be slightly lower than the actual glass transition temperature Tg of the polymer P, for example, 1 to 5 K lower. For technical reasons, the MFFT cannot be lower than 0°C, as the latex will typically freeze.

[0246] Preferably, the aqueous polymer latex of the present invention has a pH of at least 3, for example, a pH in the range of pH 3 to pH 11.5.

[0247] The aqueous polymer dispersions of the present invention typically have a solids content ranging from 30% to 75% by weight, particularly from 40% to 65% by weight, and preferably from 45% to 60% by weight. Solids content describes the proportion of non-volatile fractions. The solids content of the dispersion is determined by a balance equipped with infrared moisture analysis. In this determination, a certain amount of polymer dispersion is introduced into the instrument, heated to 140°C, and then maintained at that temperature. The measurement procedure ends once the average weight reduction falls below 1 mg within 140 seconds. 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 by the amount of added substance and its solids content and concentration.

[0248] If the polymer in the polymer latex has functional groups complementary to the functional groups of the crosslinking agent, the polymer dispersion may contain a crosslinking agent for achieving post-crosslinking of the polymer latex particles. In this context, the term "complementary" should be understood as meaning that the functional groups of the latex and the functional groups of the crosslinking agent are readily subjected to a chemical reaction that forms 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.

[0249] In addition to the polymer and optional crosslinking agents, the aqueous polymer dispersions of the present invention may also contain other components conventionally present in aqueous polymer dispersions. These other components are, for example, surfactants such as emulsifiers and protective colloids, particularly those used in the production of polymer latex, additional defoamers, etc. Other components may also be acids, bases, buffers, decomposition products from the polymerization reaction, deodorizing compounds, and chain transfer agents. Furthermore, the polymer latex may contain biocides to prevent microbial spoilage. Based on the total weight of the polymer dispersion, the amount of the respective individual component will typically not exceed 1.5 wt%. Based on the total weight of the polymer latex, the total amount of these stated components will typically not exceed 5 wt%.

[0250] Preferably, the amount of volatile organic matter, i.e. the content of organic compounds having a boiling point of up to 250°C as determined by gas chromatography under standard conditions (101,325 kPa), is less than 0.5% by weight, and particularly less than 0.2% by weight, based on the total weight of the polymer latex.

[0251] In addition to the polymer, aqueous polymer latex also contains an aqueous phase in which the polymer particles of the latex are dispersed. The aqueous phase (also known as the serum) consists essentially of water and any other water-soluble components. Based on the total weight of the aqueous phase, the total concentration of any other components will typically not exceed 10 wt%, and in particular 8% by weight.

[0252] The aqueous polymer latex of the present invention can be prepared by any method used to prepare an aqueous dispersion of a polymer made from polymeric monomer M. In particular, the aqueous polymer latex of the present invention is prepared by aqueous emulsion polymerization, especially by free radical aqueous emulsion polymerization of monomer M. 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, thereby forming free radicals in the polymerization mixture. Therefore, it is also referred to as "free radical-initiated emulsion polymerization". Procedures for free radical-initiated emulsion polymerization of monomers in aqueous media have been extensively described and are therefore well-known to those skilled in the art [see Emulsion Polymerization in the Encyclopedia of Polymer Science and Engineering, Vol. 8, p. 659 and later (1987); DC Blackley, In High Polymer Latices, Vol. 1, p. 35 and later (1966); H. Warson, The Applications of Synthetic Resin Emulsions, Chapter 5, p. 246 and later (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 Dispersionensynthetischer Hochpolymerer [Synthetic Polymer Dispersions], F. Hölscher, Springer-Verlag, Berlin (1969)]. Typical procedures for the aqueous emulsion polymerization of olefinically unsaturated monomers are also described in the patent documents discussed in the introduction of this patent application.

[0253] Radical-initiated aqueous emulsion polymerization is typically carried out by emulsifying an olefinically unsaturated monomer in an aqueous medium forming an aqueous phase, typically using a surfactant such as an emulsifier and / or a protective colloid, and polymerizing the system using at least one initiator that decays by forming free radicals and thereby initiates chain-growth addition polymerization of the olefinically unsaturated monomer M. The preparation of the aqueous polymer dispersion according to the invention may differ from this general procedure only in the specific application of the aforementioned monomers M1 to M8. It will be understood here that, for the purposes of this specification, the method should also encompass seeding, grading, single-step, and gradient methods familiar to those skilled in the art.

[0254] Free radical-initiated aqueous emulsion polymerization is triggered by free radical polymerization initiators (free radical initiators). These can, in principle, be peroxides or azo compounds. Redox initiator systems are also available. In principle, the peroxides used can be inorganic peroxides such as hydrogen peroxide, or persulfates such as monoalkali metal or dialkali metal salts or ammonium salts of persulfate, such as monosodium and disodium, potassium, or ammonium salts, or organic peroxides such as alkyl hydroperoxides, such as tert-butyl hydroperoxide, p-menthyl hydroperoxide, or cumyl hydroperoxide, as well as dialkyl or diaryl peroxides, such as di-tert-butyl or dicumyl peroxide. The azo compounds used are essentially 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 essentially the peroxides specified above. Corresponding reducing agents that can be used are sulfur compounds with low oxidation states, such as alkali metal sulfites, for example, potassium sulfite and / or sodium sulfite; alkali metal bisulfites, for example, potassium bisulfite and / or sodium bisulfite; alkali metal metabisulfites, for example, potassium metabisulfite and / or sodium metabisulfite; formaldehyde sulfoxides, for example, potassium formaldehyde sulfoxide and / or sodium formaldehyde sulfoxide; alkali metal salts of aliphatic sulfinic acids, especially potassium and / or sodium salts; and alkali metal hydrosulfides, for example, potassium hydrosulfide and / or sodium hydrosulfide; salts of polyvalent metals, such as ferric(II) sulfate, ammonium ferric(II) sulfate, ferric(II) phosphate; ethylene glycols, such as dihydroxymaleic acid, benzoin and / or ascorbic acid; and reducing sugars, such as sorbitol, glucose, fructose and / or dihydroxyacetone.

[0255] Preferred free radical initiators are inorganic peroxides, especially peroxide disulfate.

[0256] Typically, the amount of free radical initiator used is 0.05 to 2 pphm based on the total amount of monomer M, preferably 0.1 to 1 pphm based on the total amount of monomer M.

[0257] The amount of free radical initiator required for the emulsion polymerization of monomer M can initially be fully loaded into the polymerization vessel. However, it is also possible to load no free radical initiator or only a portion thereof, for example, based on a total free radical initiator weight not exceeding 30%, particularly not exceeding 20%, and then any remaining free radical initiator is added to the free radical polymerization reaction under polymerization conditions. Preferably, at least 70%, particularly at least 80%, particularly at least 90%, or the total amount of polymerization initiator, is fed into the free radical polymerization reaction under polymerization conditions. The feeding of monomer M can be carried out in one or more partial batches or continuously at a constant or varying flow rate, depending on its consumption during the free radical emulsion polymerization of monomer M.

[0258] Generally, the term "polymerization conditions" should be understood to refer to the temperatures and pressures at which free radical-initiated aqueous emulsion polymerization proceeds at a sufficient polymerization rate. These conditions are particularly dependent on the free radical initiator used. Advantageously, the type and amount of free radical initiator, polymerization temperature, and polymerization pressure are chosen such that a sufficient amount of initiating groups is always present to initiate or sustain the polymerization reaction.

[0259] Preferably, the free radical emulsion polymerization of monomer M is carried out by a so-called feed method (also known as a monomer feed method), which means that at least 80%, particularly at least 90%, or the total amount of monomer M to be polymerized is metered into the polymerization reaction under polymerization conditions during the metering time period P. The addition can be done in batches and preferably continuously at a constant or varying feed rate. The duration of time period P can depend on the production equipment and can vary from, for example, 20 minutes to 12 hours. Often, the duration of time period P will be 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 typically within the above range. The duration of individual steps is typically shorter. Preferably, at least 70%, particularly at least 80%, particularly at least 90%, or the total amount of polymerization initiator is introduced into the emulsion polymerization simultaneously with the addition of the monomer.

[0260] Aqueous free radical emulsion polymerization is typically carried out in the presence of one or more suitable surfactants. These surfactants typically contain emulsifiers and provide micelles in which polymerization occurs, and these micelles serve to stabilize monomer droplets during aqueous emulsion polymerization and also enable polymer particle growth. The surfactants used in emulsion polymerization are generally not separated from the polymer dispersion but are retained in the aqueous polymer dispersion obtainable through the emulsion polymerization of monomer M.

[0261] Surfactants can be selected from emulsifiers and protective colloids. Protective colloids, in contrast to emulsifiers, should be understood as polymeric compounds with a molecular weight greater than 2000 Daltons, while emulsifiers typically have lower molecular weights. Surfactants can be anionic, nonionic, or a mixture of nonionic and anionic surfactants.

[0262] Anionic surfactants typically have at least one anionic group, which is typically selected from phosphate, phosphonate, sulfate, and sulfonate groups. Anionic surfactants with at least one anionic group are typically used in the form of their alkali metal salts (especially their sodium salts) or their ammonium salts.

[0263] Preferred anionic surfactants are anionic emulsifiers, particularly those with at least one sulfate or sulfonate group. Similarly, anionic emulsifiers with at least one phosphate or phosphonate group can be used as the sole anionic emulsifier or in combination with one or more anionic emulsifiers with at least one sulfate or sulfonate group.

[0264] An example of anionic emulsifiers having at least one sulfate or sulfonate group is, for example,

[0265] -Alkyl sulfates, especially C8-C sulfates 22 Salts of alkyl esters, especially alkali metal salts and ammonium salts.

[0266] - Sulfated monoesters of ethoxylated alkanols, especially ethoxylated C8-C 22 Salts of sulfate monoesters of alkyl alcohols (preferably having an ethoxylation level (EO level) in the range of 2 to 40), especially alkali metal salts and ammonium salts,

[0267] -alkyl sulfonic acids, especially C8-C 22 Salts of alkyl sulfonic acids, especially alkali metal salts and ammonium salts.

[0268] - Dialkyl esters of sulfosuccinic acid, especially di-C4-C 18 Salts of alkyl esters, especially alkali metal salts and ammonium salts.

[0269] -alkylbenzene sulfonic acids, especially C4-C 22 Salts of alkylbenzene sulfonic acids, especially alkali metal salts and ammonium salts, and

[0270] - Mono- or disulfonated alkyl-substituted diphenyl ethers, for example, having a C4-C4 bond on one or both aromatic rings. 24 Salts of alkyl bis(benzenesulfonic acid) ethers, especially alkali metal salts and ammonium salts. The latter are common knowledge, for example from US-A-4,269,749, and are commercially available, for example as Dowfax. ®2A1 (Dow Chemical Company)

[0271] - Surfactants having polymerizable olefinic unsaturated double bonds as described herein, such as compounds having formulas (I)-(IV), where X and Y are SO3 - or O-SO3 - .

[0272] Examples of anionic emulsifiers containing phosphate or phosphonate groups include, but are not limited to, the following salts selected from the group consisting of:

[0273] - Mono- and dialkyl phosphates, especially C8-C 22 Salts of alkyl phosphates, especially alkali metal salts and ammonium salts.

[0274] -C2-C3-alkoxylated alkanols (preferably having an alkoxylation level in the range of 2 to 40, especially in the range of 3 to 30) phosphate monoesters, such as ethoxylated C8-C 22 -Alkyl alcohol (preferably having an ethoxylation level (EO level) in the range of 2 to 40) phosphate monoesters, propoxylated C8-C 22 -Alkyl alcohol (preferably having a propoxylation level (PO level) in the range of 2 to 40) phosphate monoesters and ethoxylated-co-propoxylated C8-C 22 Salts of phosphate monoesters of alkyl alcohols (preferably having an ethoxylation level (EO level) in the range of 1 to 20 and a propoxylation level in the range of 1 to 20), especially alkali metal salts and ammonium salts,

[0275] -alkylphosphonic acids, especially C8-C 22 Salts of alkylphosphonic acids, especially alkali metal salts and ammonium salts, and

[0276] -alkylphenylphosphonic acids, especially C4-C 22 Salts of alkylphenylphosphonic acids, especially alkali metal salts and ammonium salts.

[0277] - Surfactants having polymerizable olefinic unsaturated double bonds as described herein, such as compounds having formulas (I)-(IV), where X and Y are HPO3 and HPO4, respectively. - PO3 2 O-HPO3 - Or O-PO3 2 .

[0278] Anionic emulsifiers may also include emulsifiers having polymerizable double bonds, such as emulsifiers having formulas (I) to (IV) and their salts, particularly their alkali metal salts or ammonium salts:

[0279]

[0280] In equation (I), R 1 It is H, C1-C 20 -alkyl, C5-C 10 -Cycloalkyl, optionally C1-C 20 -alkyl-substituted phenyl, R 2 and R 2’ All are H or together are O, R 3 and R 4 It is 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-PO3 2- .

[0281] (II)

[0282] In equation (II), R represents H, C1-C 20 -alkyl, C5-C 10 -Cycloalkyl, optionally C1-C 20 -alkyl-substituted phenyl, k is 0 or 1, and X is SO3 - O-SO3 - O-HPO3 - Or O-PO3 2- .

[0283] (III)

[0284] In equation (III), R 1 It is H, C1-C 20 -alkyl, O-C1-C 20 -alkyl, C5-C 10 -Cycloalkyl, O-C5-C 10 -Cycloalkyl, optionally C1-C 20 -alkyl-substituted O-phenyl, n is an integer from 1 to 100, and Y is SO3 - HPO3 - or PO3 2- .

[0285] (IV)

[0286] In equation (IV), R 1 It is H, C1-C 20 -alkyl or 1-phenylethyl, R 2 It is H, C1-C 20-alkyl or 1-phenylethyl, A is a C2-C4 alkyldiyl, such as 1,2-ethanediyl, 1,2-propanediyl, 1,2-butanediyl, or 1,4-butanediyl, n is an integer from 1 to 100, and Y is SO3 - HPO3 - or PO3 2- .

[0287] Specific examples of copolymerizable emulsifiers having formula (I) are referred to as sulfated or phosphate esters of polyethylene glycol monoacrylate. Specific examples of copolymerizable emulsifiers having formula (I) may also be referred to as phosphonates of polyethylene glycol monoacrylate, or allyl ether sulfates. Commercially available copolymerizable emulsifiers having formula (I) are Maxemul ® Emulsifier, Sipomer ® PAM emulsifier, Latemul ® PD and ADEKA Reasoap ® PP-70.

[0288] Specific examples of copolymerizable emulsifiers having formula (II) are also referred to as alkyl allyl sulfosuccinates. A commercially available copolymerizable emulsifier having formula (II) is Trem. ® LF40.

[0289] Specific examples of copolymerizable emulsifiers having formula (III) are also referred to as branched unsaturated emulsifiers. A commercially available copolymerizable emulsifier having formula (III) is Adeka. ® Reasoap emulsifier and Hitenol ® KH.

[0290] Specific examples of copolymerizable emulsifiers having formula (IV) are also known as polyoxyethylene alkylphenyl ether sulfates and polyoxyethylene monostyrene or stilbene phenyl ether sulfates. A commercially available copolymerizable emulsifier having formula (IV) is Hitenol. ® BC and Hitenol ® AR emulsifier.

[0291] Other suitable anionic surfactants can be found in Houben-Weyl, Methoden derorganischen Chemie [Methods of Organic Chemistry], Vol. XIV / 1, Makromolekulare Stoffe [Macromolecular Substances], Georg-Thieme-Verlag, Stuttgart, 1961, pp. 192-208.

[0292] Preferably, the surfactant comprises at least one anionic emulsifier having at least one sulfate or sulfonate group. At least one anionic emulsifier having at least one sulfate or sulfonate group may be the only type of anionic emulsifier. However, a mixture of at least one anionic emulsifier having at least one sulfate or sulfonate 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 sulfonate group is preferably at least 50% by weight, based on the total weight of the anionic surfactants used in the method of the present invention. In particular, 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 method of the present invention.

[0293] Preferred anionic surfactants are anionic emulsifiers selected from the group consisting of, or mixtures thereof:

[0294] -Alkyl sulfates, especially C8-C sulfates 22 Salts of alkyl esters, especially alkali metal salts and ammonium salts.

[0295] - Sulfated monoesters of ethoxylated alkanols, especially ethoxylated C8-C 22 Salts of sulfate monoesters of alkyl alcohols (preferably having an ethoxylation level (EO level) in the range of 2 to 40), especially alkali metal salts,

[0296] -Ethoxylated alkylphenol sulfate monoesters, especially ethoxylated C4-C 18 alkylphenol sulfate monoesters (preferably with an EO level of 3 to 40),

[0297] -alkylbenzene sulfonic acids, especially C4-C 22 -alkylbenzene sulfonic acid, and

[0298] - Mono- or disulfonated alkyl-substituted diphenyl ethers, for example, having a C4-C4 bond on one or both aromatic rings. 24-alkyl bis(benzenesulfonic acid) ethers.

[0299] - Polymerizable emulsifiers of formula (III).

[0300] Particularly preferred are anionic emulsifiers, which are selected from the group consisting of, and mixtures thereof:

[0301] -Alkyl sulfates, especially C8-C sulfates 22 Salts of alkyl esters, especially alkali metal salts and ammonium salts.

[0302] - Sulfated monoesters of ethoxylated alkanols, especially ethoxylated C8-C 22 Salts of sulfate monoesters of alkyl alcohols (preferably having an ethoxylation level (EO level) in the range of 2 to 40), especially alkali metal salts,

[0303] - Mono- or disulfonated alkyl-substituted diphenyl ethers, for example, having a C4-C4 bond on one or both aromatic rings. 24 -alkyl bis(benzenesulfonic acid) ethers,

[0304] - A polymerizable emulsifier having formula (III), wherein Y is SO3 - .

[0305] In addition to the anionic surfactants mentioned above, surfactants may also contain one or more nonionic surfactants, particularly selected from nonionic emulsifiers. Suitable nonionic emulsifiers are, for example, aryl or aliphatic nonionic emulsifiers, such as ethoxylated mono, di, and trialkylphenols (EO level: 3 to 50, alkyl: C4-C). 10 ), ethoxylated long-chain alcohols (EO level: 3 to 100, alkyl: C8-C) 36 ) and poly(ethylene oxide) / poly(propylene oxide) homopolymers and copolymers. These may contain ethylene oxide units copolymerized in a random distribution or in a block form. A very suitable example is an EO / PO block copolymer. Preferred are ethoxylated long-chain alkanols, particularly alkyl C8-C alkyl groups having an average ethoxylation level of 5 to 100. 30 Those, and among these, those with linear C are particularly preferred. 12 -C 20 Alkyl groups and those with average ethoxylation levels of 10 to 50, as well as ethoxylated monoalkylphenols.

[0306] The surfactants used in the methods of the present invention typically comprise no more than 30% by weight, particularly no more than 20% by weight, of nonionic surfactants, and particularly do not contain any nonionic surfactants. 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 anionic surfactant to the total nonionic surfactant is in the range of 99:1 to 70:30, particularly 98:2 to 75:25, and particularly in the range of 95:5 to 80:20.

[0307] Preferably, the surfactant will be used in an amount such that the amount of surfactant is in the range of 0.2% to 5% by weight, particularly in the range of 0.3% to 4.5% by weight, based on the monomer M to be polymerized. In multi-step emulsion polymerization, the surfactant will be used in an amount such that the amount of surfactant is typically in the range of 0.2% to 5% by weight, particularly in the range of 0.3% to 4.5% by weight, based on the total amount of monomer polymerized in the respective step.

[0308] Preferably, at the same time as adding the monomer, the major portion, i.e., at least 80% of the surfactant used, is added to the emulsion polymerization. In particular, the monomer is added to the polymerization reaction as an aqueous emulsion containing at least 80% of the surfactant used in the emulsion polymerization.

[0309] It has been found advantageous to carry out free radical emulsion polymerization of monomer M in the presence of a seed latex. The seed latex is the polymer latex present in the aqueous polymerization medium prior to the initiation of monomer M polymerization. The seed latex can help to better control the particle size of the final polymer latex obtained in the free radical emulsion polymerization of this invention.

[0310] In principle, any polymer latex can be used as a seed latex. For the purposes of this invention, seed latexes in which the polymer particles have a relatively small particle size are preferred. In particular, the Z-mean particle size of the polymer particles of the seed latex (e.g., measured by dynamic light scattering (DLS) at 20°C (see below)) is preferably in the range of 10 to 80 nm, particularly 10 to 50 nm. Preferably, the polymer particles of the seed latex are formed from olefinically unsaturated monomers comprising at least 95% by weight of one or more monomers selected from the group consisting of: C2-C of acrylic acid. 10Alkyl esters, particularly ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, and 2-ethylhexyl acrylate; C1-C4-alkyl methacrylates, such as methyl methacrylate; mono-olefinic unsaturated nitriles, such as acrylonitrile; and vinyl aromatic monomers as defined above, such as styrene; and mixtures thereof. Specifically, the polymer particles of the seed latex are made from olefinic unsaturated monomers comprising at least 95% by weight of one or more monomers selected from the group consisting of: C1-C4-alkyl methacrylates such as methyl methacrylate, mono-olefinic unsaturated nitriles such as acrylonitrile, and vinyl aromatic monomers as defined above, such as styrene, and mixtures thereof.

[0311] Therefore, the 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 polymerization conditions are subsequently established, for example, by heating the mixture to the polymerization temperature. It may be advantageous to load at least a portion of the radical initiator into the polymerization vessel before adding monomer M. However, monomer M and the radical polymerization initiator can also be added to the polymerization vessel in parallel.

[0312] The amount of seed latex, calculated as solids, can often be based on the total weight of the monomers in the monomer composition M to be polymerized, ranging from 0.01% to 10% by weight, preferably from 0.05% to 5% by weight, and particularly from 0.05% to 3% by weight.

[0313] 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 range of 50°C to 120°C, often 60°C to 120°C, and frequently 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 therefore the polymerization temperature can exceed 100°C and can reach up to 170°C. The polymerization of monomers is typically carried out at ambient pressure, but it can also be carried out at elevated pressures. In this case, the pressure can be values ​​of 1.2, 1.5, 2, 5, 10, 15 bar (absolute pressure) or even higher. If the emulsion polymerization is carried out under reduced pressure, a pressure of 950 mbar, often 900 mbar, and frequently 850 mbar (absolute pressure) is established. Advantageously, the free radical aqueous emulsion polymerization of the present invention is carried out under ambient pressure (about 1 atm) in the absence of oxygen, for example in an inert gas atmosphere, such as nitrogen or argon.

[0314] The method 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 fed into the polymerization reaction under the polymerization conditions remains the same or nearly the same, while in multi-stage emulsion polymerization, the total composition of monomer M fed into the polymerization reaction under the polymerization conditions is changed at least once, particularly such that 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, particularly by at least 20°C or at least 40°C.

[0315] In specific embodiments, the method of the present invention is carried out as a two-stage emulsion polymerization, that is, the composition of the monomers fed into the polymerization reaction is modified once under polymerization conditions, or as a three-stage or four-stage emulsion polymerization, that is, the composition of the monomers fed into the polymerization reaction is modified two or three times under polymerization conditions.

[0316] The polymerization of monomer M may optionally be carried out in the presence of a chain transfer agent. A chain transfer agent should be understood to mean 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, dichloroethane, chloroform, bromoform, bromotrichloromethane, dibromodichloromethane, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide; and organothioides, such as primary, secondary, or tertiary aliphatic thiols, such as 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- Pentylthiol, 2-ethylbutyritin, 2-ethyl-2-butyritin, n-heptylthiol and its isomers, n-octylthiol and its isomers, n-nonylthiol and its isomers, n-decylthiol and its isomers, n-undecylthiol and its isomers, n-dodecylthiol and its isomers, n-tridecylthiol and its isomers, substituted thiols, such as 2-hydroxyethylthiol, aromatic thiols, such as benzylthiol, o-, m-, or p-methylbenzenethiol, alkyl esters of mercaptoacetic acid (thioglycolic acid), such as 2-ethylhexyl thioglycolate, alkyl esters of mercaptopropionic acid, such as octyl mercaptopropionate, and also in Polymer Handbook, 3rd edition, 1989, J. Brandrup and E. Himmergut, John Wiley & Sons, Section II. Other sulfur compounds described on pages 133 to 141, as well as aliphatic and / or aromatic aldehydes such as acetaldehyde, propionaldehyde and / or benzaldehyde, unsaturated fatty acids such as oleic acid, dienes with non-conjugated double bonds such as divinylmethane or vinylcyclohexane, or hydrocarbons with readily abstracted hydrogen atoms such as toluene.

[0317] Alternatively, a mixture of the above-mentioned chain transfer agents 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 optionally used in the method of the present invention will generally not exceed 2% by weight, particularly 1% by weight. However, it is possible that the amount of chain transfer agent added to the polymerization reaction during a certain period of time may exceed 2% by weight based on the total amount of monomer M added to the polymerization reaction during said period, and may be as high as 8% by weight, particularly up to 4% by weight.

[0318] It is often advantageous to subject the aqueous polymer dispersion obtained upon completion of polymerization of monomer M to post-treatment to reduce residual monomer content. This post-treatment is carried out chemically, for example by using a more efficient free radical initiator system to complete the polymerization reaction (referred to as post-polymerization), and / or physically, for example by stripping the aqueous polymer dispersion with steam or an inert gas. 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-A19828183, DE-A 19839199, DE-A 19840586, and DE-A 19847115. The combination of chemical and physical post-treatment has the advantage that it not only removes unconverted olefinic unsaturated monomers from aqueous polymer dispersions, but also removes other damaging volatile organic compounds (VOCs).

[0319] Because the polymer contained in the aqueous polymer dispersion may contain acidic groups from monomer M4 and optionally from the polymerization initiator, the aqueous polymer dispersion obtained by the method of the present invention is often neutralized before being formulated into a coating composition. The neutralization of the acidic groups of the polymer is achieved after polymerization and / or during polymerization using a neutralizing agent known to those skilled in the art. For example, the neutralizing agent may be added in a co-feed with the monomer to be polymerized or in a separate feed. Suitable neutralizing agents include organic amines, alkali metal hydroxides, and ammonium hydroxide. In particular, neutralization is achieved by using ammonia or alkali metal hydroxides such as sodium hydroxide or potassium hydroxide.

[0320] Furthermore, it may be suitable to formulate the polymer latex of the present invention using a post-curing agent. Ideally, such a post-curing agent (also known as a post-crosslinking agent) will induce a crosslinking reaction during and / or after film formation by forming coordination or covalent bonds with reactive sites on the surface of polymer particles.

[0321] Suitable crosslinking agents for providing post-crosslinking are, for example, compounds having at least two functional groups selected from oxazoline, amino, aldehyde, aminooxy, carbodiimide, acridine, epoxy, and hydrazide groups, or derivatives or compounds containing acetylacetyl groups. These crosslinking agents react with reactive sites in the polymer dispersion of the polymer having complementary functional groups capable of forming covalent bonds with the crosslinking agent. Suitable systems are known to those skilled in the art.

[0322] Because the polymer dispersions of the present invention contain polymers with carboxyl groups, post-crosslinking can be achieved by formulating the polymer dispersions with one or more polycarbodiimides, as described in US 4977219, US5047588, 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 leads to covalent crosslinking primarily based on N-acylurea bonds (JWTaylor and DRBassett, in EJGlass (ed.), Technology for Waterborne Coatings, ACS Conference Paper 663, Am. Chem. Soc., Washington, D.C., 1997, Chapter 8, pp. 137–163).

[0323] Similarly, since the polymer particles contained in the polymer dispersion of the present invention have carboxyl groups derived from monomer M4, a suitable post-curing agent may also be a water-soluble or water-dispersible polymer with oxazoline groups, such as the polymers described in US5300602 and WO 2015 / 197662.

[0324] Post-crosslinking can also be achieved through methods similar to EP 1227116, which describes an aqueous two-component coating composition containing an adhesive polymer having carboxylic acid and hydroxyl functional groups and a multifunctional crosslinker having functional groups selected from isocyanates, carbodiimides, acridine groups and epoxy groups.

[0325] If the polymer in the polymer dispersion contains ketone groups, for example by using monomers such as diacetone acrylamide (DAAM), then post-crosslinking can be achieved by formulating aqueous polymer dispersions with one or more dihydrazides, particularly aliphatic dicarboxylic acids such as adipate dihydrazide (ADDH), as described in US 4931494, US 2006 / 247367, and US 2004 / 143058. These components react substantially during and after film formation, although some degree of initial reaction may occur.

[0326] Other suitable reagents for achieving post-curing include

[0327] -Epoxysilanes used for carboxyl groups in crosslinked polymers;

[0328] - Dialdehydes such as glyoxal used for crosslinking urea groups or acetylacetoxy groups, such as those derived from monomers M5b and M5c as defined herein, particularly urea (meth)acrylate or acetylacetoxyethyl (meth)acrylate.

[0329] - Diamines and / or polyamines used to crosslink ketone groups or epoxy groups, such as those derived from monomers M5c or M6b as defined herein; and

[0330] -UV initiators, such as benzophenones, including benzophenone, 4-methoxybenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, acetophenones, such as 2-hydroxy-2,2-dimethylacetophenone, 2-phenyl-2,2-dimethylacetophenone, cycloalkylphenyl ketones, such as 1-benzoylcyclohexyl-1-ol (= 1-hydroxycyclohexylphenyl ketone), and benzoin and mixtures thereof, especially liquid mixtures, such as mixtures of 4-methylbenzophenone and benzophenone, mixtures of 2,4,6-trimethylbenzophenone and benzophenone, and mixtures of 1-hydroxycyclohexylphenyl ketone and benzophenone.

[0331] Suitable systems include those described in EP 355028, EP 441221, EP 0789724, US 5516453 and US5498659 and / or those that are commercially available, such as in the case of UV initiators from Omnirad and IGM Resins (e.g., Esacure TZM, Esacure TZT, Omnirad 4MBZ).

[0332] This invention also relates to water-based coating compositions containing

[0333] a) Adhesive polymers in the form of aqueous polymer latex as defined herein; and

[0334] b) At least one additional component that is conventionally used in water-based coating compositions and is not a binder.

[0335] The waterborne coating composition of the present invention can be formulated as a transparent coating or paint. In the latter case, the waterborne coating composition contains at least one inorganic pigment, which imparts a white hue or color to the resulting coating when the waterborne coating composition is used to coat a substrate.

[0336] According to the definition in German standard DIN 55944:2003-11, the pigments used for the purposes of this invention are practically insoluble, finely dispersed, organic or preferably inorganic colorants. Examples of pigments are particularly inorganic pigments, such as white pigments like titanium dioxide (CI Pigment White 6), and also coloring pigments, for example...

[0337] - Black pigments, such as iron oxide black (CI Pigment Black 11), iron manganese black, spinel black (CI Pigment Black 27), and carbon black (CI Pigment Black 7).

[0338] - Coloring 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); molybdate red (CI pigment red 104); ultramarine red,

[0339] - Iron oxide brown, mixed brown, spinel and corundum phase (CI pigment brown 24, 29 and 31), chrome orange;

[0340] - 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; Neapolitan yellow; Bismuth vanadate (CI Pigment Yellow 184).

[0341] - 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.

[0342] Waterborne coating compositions may also contain one or more fillers. Examples of suitable fillers are aluminosilicates such as feldspar, silicates such as kaolin, talc, mica, magnesite, alkaline earth metal carbonates such as calcium carbonate (e.g., in the form of calcite or chalk), magnesium carbonate, dolomite, alkaline earth metal sulfates such as calcium sulfate, silica, etc. Finely crushed fillers are naturally preferred in the coating compositions of the present invention. Fillers can be used as individual components. However, in practice, filler mixtures have been found to be particularly useful, such as calcium carbonate / kaolin or calcium carbonate / talc. Glossy paints typically contain only a small amount of very finely crushed filler or no filler at all. Fillers also include matting agents that significantly reduce gloss as needed. Matting agents are typically transparent and can be organic or inorganic. Examples of matting agents are inorganic silicates, such as Syloid from WR Grace & Company. ® The brand and Acematt from Evonik GmbH ® Brands. Organic matting agents are available, for example, from BYK-Chemie GmbH under the brand name Ceraflour. ® Brands and Ceramat ®The brand, and from Deuteron GmbH, under the name Deuteron MK ® Brand acquisition.

[0343] The ratio of pigments and fillers in a waterborne coating composition can be described in a manner known per se by pigment volume concentration (PVC). PVC describes the percentage ratio of the volume of pigment (VP) and the volume of filler (VF) relative to the total volume, which consists of the volume of binder (VB), the volume of pigment (VP), and the volume of filler (VF) in the dried coating film: PVC [%] = (VP + VF) x 100 / (VP + VF + VB).

[0344] If the waterborne coating compositions are formulated as paints, they typically have a pigment volume concentration (PVC) of at least 5%, particularly at least 10%, and will typically not exceed 90%, particularly 85%. In the preferred set of embodiments, the PVC will not exceed a value of 60%, particularly 50%, and specifically in the range of 5% to 60% or 5% to 50%. However, the inventive effects of the polymer dispersions also manifest in varnishes, which typically have a pigment / filler content of less than 5% by weight based on the varnish, and correspondingly have less than 5% PVC. In yet another set of embodiments, the PVC will be in the range of >60% to 90%, particularly in the range of 65% to 85%.

[0345] According to one set of embodiments, the waterborne coating compositions of the present invention are designed as paints containing white pigments—that is, they comprise at least one white pigment and optionally one or more fillers. As white pigments, they particularly include titanium dioxide (preferably in rutile form), optionally in combination with one or more fillers. Particularly preferably, the coating compositions of the present invention comprise a white pigment, more particularly titanium dioxide (preferably in rutile form), and one or more fillers (e.g., chalk, talc, or mixtures thereof).

[0346] In another preferred group of embodiments, the waterborne coating compositions of the present invention are designed as clear coatings or wood stain formulations. Compared to paints, clear coatings are essentially free of pigments and fillers, while wood stains contain very little filler, i.e., they have less than 5% PVC.

[0347] According to specific embodiments, the present invention also relates to a waterborne coating composition (hereinafter also referred to as a waterborne coating composition) comprising:

[0348] i) at least one aqueous polymer latex as defined above; and

[0349] ii) Titanium dioxide pigment.

[0350] According to another specific set of embodiments, the present invention also relates to the use of aqueous polymer latex as a binder in aqueous coating compositions containing titanium dioxide pigments.

[0351] In the above embodiments, an aqueous polymer latex is combined with a TiO2 pigment paste or slurry. The TiO2 concentration of the aqueous TiO2 pigment paste or slurry used to prepare the aqueous coating composition is typically in the range of 30% to 85% by weight, often 40% to 80% by weight, and in each case based on the total weight of the aqueous TiO2 pigment paste or slurry. The titanium dioxide pigment used to prepare the aqueous dispersion of the pigment paste or slurry can be any TiO2 pigment conventionally used in coating compositions, particularly aqueous coating compositions. Often, TiO2 pigments in which the TiO2 particles are preferably in rutile form are used. In another preferred embodiment, the TiO2 particles may also be coated with, for example, aluminum, silicon, and zirconium compounds.

[0352] Typically, the weight ratio of the polymer to the titanium dioxide pigment is in the range of ≥ 0.1 : 5.0 to ≤ 5.0 : 0.1; preferably, the weight ratio of the polymer to the titanium dioxide pigment is in the range of ≥ 0.5 : 5.0 to ≤ 5.0 : 0.5; particularly more preferably, the weight ratio of the polymer to the titanium dioxide pigment is in the range of ≥ 0.5 : 3.0 to ≤ 3.0 : 0.5 and especially in the range of ≥ 0.5 : 1.5 to ≤ 1.5 : 0.5.

[0353] Preferably, the titanium dioxide pigment has an average primary particle size in the range of ≥ 0.1 µm to ≤ 0.5 µm, as determined by light scattering or electron microscopy.

[0354] Typically, waterborne coating compositions further comprise at least one additive selected from the group consisting of: thickeners, defoamers, leveling agents, film-forming aids, biocides, wetting agents or dispersants, fillers, and coalescing agents.

[0355] The waterborne coating composition can be simply prepared by mixing TiO2 pigment powder or an aqueous paste or slurry of TiO2 pigment with the waterborne polymer latex of the present invention, preferably by applying shear to the mixture, for example by using a solvent conventionally used for preparing waterborne paints. Alternatively, an aqueous paste or slurry of TiO2 pigment and the waterborne polymer latex of the present invention can be prepared and then incorporated into another polymer latex or any other polymer latex binder of the present invention, or mixed with another polymer latex or any other polymer latex binder of the present invention.

[0356] Aqueous dispersions of polymeric composites can also be prepared by incorporating the aqueous polymeric latex of the present invention as a binder or co-binder into an aqueous base formulation of a paint already containing TiO2 pigment, for example by mixing the aqueous polymeric latex of the present invention with a pigment formulation already containing other additives conventionally used in paint formulations.

[0357] To stabilize TiO2 pigment particles in aqueous pigment pastes or slurries, mixing may optionally be carried out in the presence of additives (such as dispersants) conventionally used in aqueous pigment pastes or slurries. Suitable dispersants include, but are not limited to, polyphosphates such as sodium polyphosphate, potassium polyphosphate, or ammonium polyphosphate, alkali metal salts and ammonium salts of acrylic homopolymers or copolymers or maleic anhydride polymers, polyphosphonates such as sodium 1-hydroxyethane-1,1-diphosphonate, and naphthalene sulfonates, especially their sodium salts.

[0358] In each case, based on the total weight of the aqueous polymer latex, the polymer concentration in the aqueous polymer latex used to prepare the aqueous dispersion of the polymer composite 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.

[0359] 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 and / or fillers other than TiO2 pigments, as described above.

[0360] Preferably, the waterborne coating composition comprises at least one waterborne polymer latex as defined herein, and further comprises a rheology modifier. Suitable rheology modifiers include associative thickener polymers and non-associative rheology modifiers. The waterborne liquid composition preferably comprises a thickener selected from the group consisting of associative thickeners and non-associative thickeners and combinations thereof.

[0361] Associative thickener polymers are well-known and frequently described in scientific literature, such as E.J. Challer et al., “Associative Thickeners” in Handbook of Coating Additives, Volume 2 (edited by L.J. Calbo), Marcel Decker 192, pp. 105-164, and “PUR-Verdicker” in Additives for Coatings (edited by J. Bielemann), Wiley 2000, pp. 50-58. NiSAT thickener polymers of the HEUR and HMPE types are also described in patent documents such as US 4,079,028, US 4155,892, EP 61822, EP307775, WO 96 / 31550, EP 612329, EP 1013264, EP 1541643, EP 1584331, EP 2184304, DE4137247, DE 102004008015, DE 102004031786, US 2011 / 0166291, and WO 2012 / 052508. In addition, associative thickener polymers are commercially available.

[0362] Associative thickener polymers include anionic acrylate-type thickener polymers, the so-called HASE polymers (hydrophobically modified polyacrylate thickeners), which are copolymers of acrylic acid and alkyl acrylate monomers, wherein the alkyl group of the alkyl acrylate can have 6 to 24 carbon atoms. Associative thickener polymers also include nonionic associative thickeners, the so-called NiSAT thickeners (nonionic synthetic associative thickeners), which are typically linear or branched block copolymers having at least one internal hydrophilic moiety, particularly a polyether moiety, particularly at least one polyethylene oxide moiety, and two or more terminal hydrocarbon groups, each of which has at least 4 carbon atoms, particularly 4 to 24 carbon atoms, such as linear or branched alkyl groups having 4 to 24 carbon atoms or alkyl-substituted phenyl groups having 7 to 24 carbon atoms. NiSAT thickeners include hydrophobically modified polyethylene oxide urethane rheology modifiers (also known as HEUR or PUR thickeners) and hydrophobically modified polyethylene oxide (also known as HMPE).

[0363] The amount of associative thickener polymer will depend on the desired viscosity profile and is often in the range of 0.05% to 2.5% by weight, particularly 0.1% to 2% by weight, and especially 0.2% to 2% by weight of thickener based on latex paint.

[0364] Suitable non-associative rheology modifiers are, in particular, cellulose-based thickeners, especially hydroxyethyl cellulose, and also acrylate-based emulsion (ASE) thickeners. Among non-associative rheology modifiers, non-associative cellulose-based thickeners are preferred.

[0365] The total amount of thickener polymer will depend on the desired viscosity profile and is often in the range of 0.05% to 6% by weight based on latex paint, particularly 0.1% to 5.5% by weight, and especially 0.15% to 5% by weight.

[0366] The waterborne coating compositions of the present invention may also contain conventional additives. Conventional additives will depend on the type of coating in a well-known manner and include, but are not limited to:

[0367] - Wetting agents or dispersants

[0368] Film-forming aids, also known as coalescing agents.

[0369] - Leveling agent,

[0370] -UV stabilizer,

[0371] - biocides and

[0372] - Defoamer / Degassing agent.

[0373] Suitable wetting or dispersing agents are, for example, sodium polyphosphate, potassium polyphosphate or ammonium polyphosphate, alkali metal salts and ammonium salts of acrylic acid copolymers or maleic anhydride copolymers, polyphosphonates such as sodium 1-hydroxyethane-1,1-bisphosphonate, and naphthalene sulfonates, especially their sodium salts.

[0374] Suitable film-forming aids are solvents and plasticizers. Compared to solvents, plasticizers have lower volatility and preferably have a boiling point above 250°C at 1013 mbar, while solvents have higher volatility and preferably have a boiling point below 250°C at 1013 mbar. Suitable film-forming aids include, for example, white alcohol, pine oil, propylene glycol, ethylene glycol, butylene glycol, butylene glycol acetate, butylene glycol diacetate, butyl diethylene glycol, butyl carbitol, 1-methoxy-2-propanol, and 2,2,2-trimethyl-1,3-pentanediol monoisobutyrate (Texanol). ® ) and glycol ethers and esters, such as those from BASF SE (BASF SE) using Solvenon ® and Lusolvan® and Loxanol ® The name is available for commercial purchase, and from Dow under the name Dowanol. ® The product name is commercially available. Based on the total formulation, the amount is preferably < 5% by weight and more preferably < 1% by weight. The formulation is also entirely possible without film-forming aids. Often, coating compositions do not require any film-forming aids.

[0375] Other suitable additives and components are described, for example, by J. Bieleman in "Additives for Coatings," Whiley-VCH, Weinheim 2000; by TCPatton in "Paint Flow and Pigment Dispersions," 2nd edition, John Whiley & Sons 1978; and by M. Schwartz and R. Baumstark in "Water-based Acrylates for Decorative Coatings," Curt R. Vincentz Verlag, Hanover 2001.

[0376] The waterborne coating composition of the present invention can also be formulated as a low-VOC paint. In this case, the concentration of volatile compounds in the coating composition is preferably less than 0.1 wt.-%, more preferably less than 0.05 wt.-%, based on the total amount of the waterborne coating composition. For the purposes of the present invention, volatile compounds are compounds having a boiling point of less than 250°C at 1013 mbar.

[0377] The water-based coating compositions of the present invention are 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 calcined gypsum, raw gypsum, gypsum board or concrete, wood, wood-based materials, metal, wallpaper or plastic such as PVC.

[0378] Water-based coating compositions can be applied to the substrate to be coated in conventional ways, such as by brushing or rolling, by spraying, by dipping, by rolling, or by applying with a stick to the desired substrate. Preferred application is by brushing and / or by rolling.

[0379] Typically, the coating of the substrate is carried out in such a manner that the substrate is first coated with the aqueous coating composition of the present invention, and then the aqueous coating thus obtained is subjected to a drying step, particularly in a temperature range of ≥ -10°C and ≤ +50°C, advantageously ≥ +5°C and ≤ +40°C, and especially advantageously ≥ +10°C and ≤ +35°C.

[0380] 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, the coating possesses good adhesion properties such as high dry alkyd adhesion, good opacity, high anti-blocking properties, good detergency, high wet scrub resistance, and low dust accumulation.

[0381] The present invention also relates to an aqueous adhesive composition containing

[0382] a) Adhesive polymers in the form of aqueous polymer latex as defined herein; and

[0383] b) At least one additional component that is conventionally used in water-based adhesive compositions and is not an adhesive.

[0384] In addition to polymer latex, the aqueous adhesive compositions of the present invention typically contain more than one additional ingredient well known in the art, such as additives, including but not limited to, rheology modifiers, plasticizers, tackifiers, defoamers, wetting agents, biocides, and adhesion promoters, wherein the rheology modifiers, plasticizers, defoamers, wetting agents, and biocides may be selected from those mentioned above. The aqueous adhesive compositions of the present invention may contain additional or other additional ingredients also well established in the art. Formulations of the aqueous adhesive compositions of the present invention suitable for a particular adhesive application comprise a specific adhesive polymer and at least one, usually two or more, specific additional ingredients. The exact properties of all these components and the amounts available in the preparation of such formulations can generally be determined in a manner known per se. Example

[0385] The present invention will be illustrated by the following non-limiting examples.

[0386] 1. Vocabulary List:

[0387]

[0388] As used herein and below, the terms “room temperature” and “ambient temperature” mean a temperature in the range of 22°C to 23°C.

[0389] 2. Analysis of polymer latex

[0390] 2.1 Solid content

[0391] Solids content was determined by drying a specified amount of aqueous polymer dispersion (approximately 2 g) to constant weight in an aluminum crucible with an inner diameter of approximately 5 cm at 130°C for 2 hours. Two separate measurements were performed. The values ​​reported in the examples are the average of the two measurements.

[0392] 2.2 Particle size

[0393] Unless otherwise stated, the average particle size of the polymer latex was determined using Malvern HPPS by dynamic light scattering (DLS) as described above.

[0394] 2.3 Glass transition temperature Tg

[0395] The glass transition temperature was determined by DSC method (differential scanning calorimetry, 20 K / min, midpoint measurement, DIN53765:1994-03) using a DSC instrument (Q 2000 series from TA Instruments).

[0396] 2.4 pH Measurement

[0397] pH was measured on the reaction mixture using a pH meter.

[0398] 3. Ingredients

[0399] The following components are used in examples of this invention:

[0400]

[0401] 1-Hexyl acrylate can be prepared by esterification of acrylic acid with 1-hexanol via a procedure similar to that described in DE 10246869.

[0402] 1-Heptyl acrylate was prepared by esterification.

[0403] In a heated 4L double-walled glass reactor equipped with an anchor stirrer, water separator, dense cooler, heating element, and lean air inlet, 818 g of n-hexanol was placed. 87.7 g of 3.33% MeHQ aqueous solution, 692 g of pure acrylic acid, 30.4 g of p-toluenesulfonic acid monohydrate, 8.8 g of 5% copper(II) acetate solution, 7.3 g of hypophosphite (50%), and 644 g of cyclohexane were added. The mixture was heated at a bath temperature of 105°C with stirring and lean air, thereby gradually increasing the bath temperature to 125°C during the reaction. The azeotrope of cyclohexane and water was distilled off at a tank temperature of 80°C–104°C. After 5.3 h, an additional 29 g of acrylic acid was added. Within 6.5 h, 284 g of water was distilled off, and the reaction was stopped. The reaction mixture was extracted with 1 kg of ice / water mixture at approximately 65°C. After phase separation, 195 g of 12.5% ​​NaOH and 300 g of water were added, and the aqueous phase was discarded after separation. Subsequently, two additional extractions were performed, each using 700 mL of 15% NaCl solution. The crude solution was mixed with 100 mg of MeHQ and then concentrated on a rotary evaporator at 60°C to 85 mbar. The resulting product was filtered through a pleated filter.

[0404] Hexyl acrylate was obtained in a yield of 1112 g (89%) with a GC purity of 94.

[0405] 4. Preparation Examples

[0406] 4.1 Adhesive Examples

[0407] Example E1 of the present invention

[0408] Adhesives based on polymers containing 1-hexyl acrylate and methyl methacrylate

[0409] 244.3 g of deionized water and 27.3 g of polystyrene seed dispersion (33 wt%, particle size: 30 nm) were charged into a reactor equipped with a stirrer, temperature controller, nitrogen inlet, and multiple injection possibilities. The reaction mixture was purged with nitrogen and heated to 85°C. At 85°C, 5.0 g of feed 2 was added. After 5 min, feed 1 and feed 2 were added over 180 min.

[0410] - Feed 1: 400.5 g deionized water, 18.5 g Dowfax 2A1, 20.8 g Lutensol TO 82, 6.9 g acrylic acid, 13.9 g acrylamide (50 wt% aqueous solution), 289.5 g 1-hexyl acrylate, and 394.2 g methyl methacrylate.

[0411] - Feed 2: 19.8 g of sodium persulfate aqueous solution (7 wt%).

[0412] Post-polymerization of the reaction mixture was carried out at 85°C for 30 min. Then, feed 3 and feed 4 were added over 60 min.

[0413] - Feed 3: 6.9 g of tert-butyl hydroperoxide aqueous solution (10 wt%).

[0414] - Feed 4: 6.2 g of Rongalit C aqueous solution (10 wt%).

[0415] The reaction mixture was then cooled to ambient temperature and neutralized with sodium hydroxide to pH 8-9.

[0416] Tg (dried dispersion): 21°C

[0417] Average particle size: 130 nm

[0418] Solid content: 47.4 wt%

[0419] Comparison Example C1

[0420] Adhesives based on polymers containing n-butyl acrylate and methyl methacrylate

[0421] 244.3 g of deionized water and 27.3 g of polystyrene seed dispersion (33 wt%, particle size: 30 nm) were charged into a reactor equipped with a stirrer, temperature controller, nitrogen inlet, and multiple injection possibilities. The reaction mixture was purged with nitrogen and heated to 85°C. At 85°C, 5.0 g of feed 2 was added. After 5 min, feed 1 and feed 2 were added over 180 min.

[0422] - Feed 1: 400.5 g deionized water, 18.5 g Dowfax 2A1, 20.8 g Lutensol TO 82, 6.9 g acrylic acid, 13.9 g acrylamide (50 wt% aqueous solution), 346.4 g methyl methacrylate, and 332.6 g n-butyl acrylate.

[0423] - Feed 2: 19.8 g of sodium persulfate aqueous solution (7 wt%).

[0424] Post-polymerization of the reaction mixture was carried out at 85°C for 30 min. Then, feed 3 and feed 4 were added over 60 min.

[0425] - Feed 3: 6.9 g of tert-butyl hydroperoxide aqueous solution (10 wt%).

[0426] - Feed 4: 6.2 g of Rongalit C aqueous solution (10 wt%).

[0427] The reaction mixture was then cooled to ambient temperature and neutralized with sodium hydroxide to pH 8-9.

[0428] Tg (dried dispersion): 20°C

[0429] Average particle size: 133 nm

[0430] Solid content: 49.4 wt%

[0431] 4.2 Examples of Preparations

[0432] Example E2 of the present invention

[0433] Formulations of semi-gloss varnishes containing adhesives from Example E1

[0434] Mix 200.0 g of Kronos 4311 pigment with 15.0 g of water. Add 1.75 g of AMP-95 neutralizer (Angus Chemicals), 5.0 g of propylene glycol (Unyler), 2.0 g of Foamstar 2420 defoamer (BASF), 10.0 g of Tamol 165 A dispersant (Dow), and 3.0 g of Hydropalat WE3320 wetting agent (BASF) at low stirring speed. Add 1.5 g of Attagel 50 (BASF), 25.0 g of Minex 10 (Silicon Biotech) filler, 125.0 g of Kronos 4311 pigment, 88.0 g of water, and 20.0 g of Aquaflow NHS-310 (Ashland) nonionic associative thickener at high stirring speed and mix for 30 min. The mixture was filtered through a 400µm filter and then added to a combination of 510.4 g of binder from Example E1, 25.0 g of Ropaque UltraE polymer pigment (Dow), and 2.0 g of Foamstar 2420 defoamer (BASF) and stirred for 5 min. 9.0 g of Texanol coalescing agent (Eastman) and 7.4 g of Optifilm 400 coalescing agent (Eastman) were added and mixed for 5 min. Then, 2.0 g of Proxel AQ biocide (Lonza), 3.0 g of Polyphase 663 fungicide (Troy), and 5.0 g of Rheolate CVS 10 nonionic associative thickener (Hymens) were added and mixed for 5 min. Finally, 2.0 g of Acrysol RM 895 nonionic associative thickener (Dow) was added and the mixture was stirred at medium speed for 30 min.

[0435] Comparison Example C2

[0436] Formulations of semi-gloss varnishes containing the binder from Example C1

[0437] Mix 200.0 g of Kronos 4311 pigment with 15.0 g of water. Add 1.75 g of AMP-95 neutralizer (Angus Chemicals), 5.0 g of propylene glycol (Unyler), 2.0 g of Foamstar 2420 defoamer (BASF), 10.0 g of Tamol 165 A dispersant (Dow), and 3.0 g of Hydropalat WE3320 wetting agent (BASF) at low stirring speed. Add 1.5 g of Attagel 50 (BASF), 25.0 g of Minex 10 (Silicon Biotech) filler, 125.0 g of Kronos 4311 pigment, 114.7 g of water, and 20.0 g of Aquaflow NHS-310 (Ashland) nonionic associative thickener at high stirring speed and mix for 30 min. The mixture was filtered through a 400µm filter and then added to a combination of 489.7 g of binder from Example C1, 25.0 g of Ropaque UltraE polymer pigment (Dow), and 2.0 g of Foamstar 2420 defoamer (BASF) and stirred for 5 min. 9.0 g of Texanol coalescing agent (Eastman) and 4.0 g of Optifilm 400 coalescing agent (Eastman) were added and mixed for 5 min. Then, 2.0 g of Proxel AQ biocide (Lonza), 3.0 g of Polyphase 663 fungicide (Troy), and 5.0 g of Rheolate CVS 10 nonionic associative thickener (Hymens) were added and mixed for 5 min. Finally, 2.0 g of Acrysol RM 895 nonionic associative thickener (Dow) was added and the mixture was stirred at medium speed for 30 min.

[0438] 4.3 Application Characteristics

[0439] The following applied characteristics were measured.

[0440] Low shear viscosity:

[0441] The low-shear viscosity was measured according to ASTM D562 7 days after preparation. The results are as follows:

[0442]

[0443] Opacity:

[0444] A coating film was prepared on a Leneta 3B black and white sealable squeegee using a 3-mil doctor blade. The film was dried at room temperature for 24 hours. Opacity was determined spectrophotometrically as the ratio of reflected light from the black portion of the Leneta card to that reflected from the dried coating on the white portion. Opacity indicates the coating's ability to cover black surfaces. The results are as follows:

[0445]

[0446] Compared to C2, E2 has slightly improved opacity.

[0447] König pendulum hardness:

[0448] The König pendulum hardness was measured according to ASTM D4366 using aluminum as the coated substrate. Evaluation was performed after 7 days. The following results each reflect the average number of oscillations from three measurements.

[0449]

[0450] Compared to C2, E2 shows a significant improvement in hardness.

[0451] Cleansing properties:

[0452] Detergency was measured according to ASTM D4828. The results of the coating from E2 for pencils, lipsticks, crayons, ballpoint pens, red wine, ketchup, coffee, and mustard were comparable to those of the coating from C2 (visual inspection).

[0453] Dust accumulation property:

[0454] Wash the glaze off the yellow pine surface with water and let it dry overnight. Divide the substrate into multiple sections depending on the number of samples to be tested. Apply the test varnish sample using a suitable brush at a natural application rate. Allow the coatings to cure at room temperature for 4 hours and 24 hours, respectively. Then, cover half of the coated area with a 2-inch layer of dried dirt (Arizona dirt or Carpet dirt). Let the panel sit for 15 minutes, then tilt it vertically and tap it to loosen the dirt. Gently brush the dirty areas of each sample (15 light wipings).

[0455] The dust accumulation properties of the coating from E2 are comparable to those of the coating from C2 (visual assessment).

[0456] Scrub resistance:

[0457] Scrub resistance is measured according to ASTM D2486. Determine the number of scrub cycles required until failure occurs.

[0458]

[0459] The scrub resistance of the coating from E2 is slightly reduced compared to the coating from C2.

Claims

1. An aqueous polymer latex of a copolymer, which can be obtained by aqueous emulsion polymerization of olefinically unsaturated monomers M, wherein these olefinically unsaturated monomers M contain... i. Based on the total amount of monomer M, 5% to 90% by weight of monomer M1, which is 1-hexyl acrylate; ii. At least one monomer M2, comprising 0% to 70% by weight of monomer M, selected from C2-C5-alkyl esters of acrylic acid other than tert-butyl acrylate, and C7-C4-alkyl esters of acrylic acid. 20 -C5-C of alkyl esters and methacrylic acid 20 -Alkyl esters and mixtures thereof; iii. At least one monomer M3, comprising 5% to 70% by weight of monomer M, selected from tert-butyl acrylate, C1-C4-alkyl esters of methacrylate, and C5-C4-alkyl esters of acrylic acid. 20 -Cycloalkyl esters, C5-C of methacrylic acid 20 -Cycloalkyl esters, C5-C of acrylic acid 20 -Cycloalkyl methyl esters, C5-C of methacrylic acid 20 -Cycloalkyl methyl esters, wherein the cycloalkyl group in the monomer is monocyclic, bicyclic, or tricyclic, and wherein one or two non-adjacent CH2 moieties of the cycloalkyl group can be replaced by oxygen atoms, and wherein the cycloalkyl group can be unsubstituted or have 1, 2, 3, or 4 methyl groups, as well as monovinyl aromatic monomers, methylene-γ-butyrolactone, and mixtures thereof; and iv. At least one monomer M4, selected from monoene unsaturated monomers having an acidic group; The total amount of monomers M1 and M2 is in the range of 10% to 90% by weight of the total amount of olefin-based unsaturated monomer M, and the total amount of monomers M1, M2 and M3 is at least 90% by weight of the total amount of olefin-based unsaturated monomer M.

2. The aqueous polymer latex as described in claim 1, wherein, In these monomers M1, at least the carbon atom of the 1-hexyl group is of biological origin.

3. The aqueous polymer latex as claimed in any one of the preceding claims, wherein, The monomer M2 is selected from the group consisting of n-butyl acrylate, isobutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate and mixtures thereof.

4. The aqueous polymer latex as described in claim 3, wherein, At least the carbon atoms of the isobutyl group of isobutyl acrylate and / or the 2-octyl group of 2-octyl acrylate are of biological origin.

5. The aqueous polymer latex as claimed in any one of the preceding claims, wherein, The monomer M3 contains methyl methacrylate.

6. The aqueous polymer latex as described in claim 5, wherein, The monomer M3 is selected from methyl methacrylate and combinations of methyl methacrylate and at least one other monomer M3, wherein the other monomer M3 is selected from tert-butyl acrylate, n-butyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, α-methylene-γ-butyrolactone and styrene.

7. The aqueous polymer latex as claimed in any of the preceding claims, wherein, The total amount of monomers M1 and M2 is in the range of 20% to 80% by weight of the total amount of olefin-based unsaturated monomer M, and the total amount of monomer M3 is in the range of 15% to 70% by weight of the total amount of olefin-based unsaturated monomer M.

8. The aqueous polymer latex as claimed in any of the preceding claims, wherein, The amount of monomer M4 is in the range of 0.05% to 5% by weight of the total amount of olefin-based unsaturated monomer M.

9. The aqueous polymer latex as claimed in any one of the preceding claims, wherein, These monomers M4 are selected from acrylic acid, methacrylic acid, itaconic acid, and combinations thereof.

10. The aqueous polymer latex as claimed in any of the preceding claims, wherein, These monomers M further comprise at least one mono-olefinically unsaturated nonionic monomer M5, which has a solubility of at least 60 g / L in deionized water at 20°C and 1 bar.

11. 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 formamide, urea, and ketone groups and combinations thereof.

12. The aqueous polymer latex as claimed in any of the preceding claims, wherein, These monomers M are composed of the following: i. 1-Hexyl acrylate, based on 5% to 90% by weight of monomer M as monomer M1; ii. At least one monomer M2, comprising 0% to 70% by weight of monomer M; iii. At least one monomer M3, comprising 15% to 70% by weight of monomer M; iv. Based on the total amount of monomer M, from 0.05% to 5% by weight of one or more mono-olefinic unsaturated monomers M4, which are selected from mono-olefinic unsaturated monomers having acidic groups; v. One or more nonionic monomers M5, comprising 0% to 9.95% by weight of the total weight of these monomers M, having a solubility of at least 60 g / L in deionized water at 20°C and 1 bar.

13. The aqueous polymer latex as claimed in any of the preceding claims, wherein, The polymer particles contain a polymer phase having a glass transition temperature Tg in the range of -40°C to +40°C.

14. A method for producing an aqueous polymer latex as described in any of the preceding claims, the method comprising performing an aqueous emulsion polymerization of monomer M.

15. Use of the aqueous polymer latex as a binder in any one of claims 1 to 13.

16. A water-based coating composition containing a) an adhesive copolymer in the form of an aqueous polymer latex as described in any one of claims 1 to 13; and b) At least one additional component that is conventionally used in water-based coating compositions and is not a binder.

17. The coating composition of claim 16, wherein the coating composition is a latex paint, particularly a latex paint for architectural coatings, wood coatings or wood staining compositions, or a latex paint for interior coatings.

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