Water-based polymer latexes of film-forming copolymers suitable as binders in water-based coating compositions

Abstract

The present invention relates to an aqueous polymer latex of a film-forming copolymer obtained by aqueous emulsion polymerization of ethylenically unsaturated monomers M, i. from 5 to 70% by weight, in particular from 10 to 60% by weight, of at least one monomer M1 chosen from cyclopentyl acrylate, cyclopentyl methacrylate and mixtures thereof, based on the total amount of monomers M; ii. 20 to 90% by weight, in particular 30 to 80% by weight, of C2-C acrylic acid, excluding tert-butyl acrylate, based on the total amount of monomers M 20 -C5-C alkyl esters and methacrylic acid 20 at least one monomer M2 selected from alkyl esters, as well as mixtures thereof; iii. 0 to 40% by weight, in particular 0 to 35% by weight, of one or more monomers M3 selected from tert-butyl acrylate, C1-C4-alkyl esters of methacrylic acid, cyclohexyl methacrylate, isobornyl methacrylate and monovinyl aromatic monomers, and mixtures thereof, based on the total amount of monomers M; wherein the total amount of monomers M1 and M3 is in the range of 5 to 70% by weight, in particular at least 10 to 60% by weight, based on the total amount of ethylenically unsaturated monomers M, and the total amount of monomers M1, M2 and M3 is at least 85% by weight, based on the total amount of ethylenically unsaturated monomers M. The present invention also relates to a process for producing the aqueous polymer latexes of the present invention, which process comprises carrying out an aqueous emulsion polymerization of monomer M. The present invention also relates to the use of these polymer latexes as binders in water-based coating compositions.

Description

[Technical Field]

[0001] The present invention relates to aqueous polymer latexes of film-forming copolymers obtained by aqueous emulsion polymerization of ethylenically unsaturated monomers M containing a combination of (meth)acrylate esters as monomers. The present invention also relates to a process for producing such polymer latexes and to the use of these polymer latexes as binders in water-based coating compositions. Furthermore, the present invention relates to water-based coating compositions containing a binder polymer in the form of an aqueous polymer latex as defined herein and at least one additional component conventionally used in water-based coating compositions that is not a binder. [Background technology]

[0002] Polymer latexes, also known as polymer dispersions, are commonly known as binders or co-binders, particularly for coating compositions. As binders or co-binders in coating compositions, one of the important requirements is that they provide hardness and anti-blocking properties to the coating and adhesion to the coating surface. In addition, polymer latexes must provide good opacity, good humidity scrub resistance, good stain removal properties, low stain adhesion, and low water absorption.

[0003] Despite many advances, providing polymer dispersions with a balanced application profile remains a challenge, as not only application properties but also the stability of the polymer dispersion must be considered. In particular, it is difficult to simultaneously achieve different coating property requirements through the binder. Generally, attempts to improve one coating property by changing the polymer composition of the binder significantly degrade other properties of the coating.

[0004] Although polymer dispersions described in the art have certain advantages in one or more aspects, they do not necessarily have a well-balanced application profile. Apart from that, they are based solely on monomers prepared from fossil sources. In view of the ongoing discussion on 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 in part from renewable raw materials, such as plants, plant parts, plant waste, biomass, etc. These products are called bio-based, 14 These materials are characterized by a traceable content of C carbon. These materials can also be converted into suitable feedstocks, such as bionaphtha, as described, for example, in EP 2 290 045 or EP 2 290 034. Such feedstocks typically enter chemical production systems, such as steam crackers, where they are converted into products along the chemical value chain, such as acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, etc. The renewable material content of these products can be defined and allocated to these products using a mass balance approach.

[0005] WO 2014 / 207389 describes the use of 2-octyl acrylate from renewable resources in the production of polymer latexes. The polymer latexes are proposed as binders. However, because homopolymers of 2-octyl acrylate have glass transition temperatures below -40°C, a large amount of 2-octyl acrylate in the latex-forming monomers results in a low glass transition temperature of the resulting polymer. Therefore, a latex with a suitable glass transition temperature requires a significant amount of conventional fossil-based monomers.

[0006] WO 2018 / 118221 describes copolymer latexes containing a high content of biorenewable carbon monomers whose homopolymers have high glass transition temperatures, particularly isobornyl methacrylate. However, isobornyl methacrylate can cause problems during emulsion polymerization and can result in unstable polymer latexes (see, for example, O. Llorente et al., Progress in Organic Coatings 172 (2022) 107137).

[0007] WO 2022 / 018013 describes a polymer latex 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 result in coatings with improved coating properties, such as improved whitening resistance, water absorption, and flexibility. Isobutyl acrylate and isoamyl acrylate—at least with respect to their alkanol moieties—can be obtained from biological sources, thereby reducing the amount of fossil carbon in the polymer latex.

[0008] JP 11171927A describes aqueous polymer dispersions containing polymers based on dicyclopentyl (meth)acrylate, which have a number average molecular weight of 1000 to 1,000,000 and exhibit low odor and high heat resistance. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] European Patent Application Publication No. 2 290 045 [Patent Document 2] European Patent Application Publication No. 2 290 034 [Patent Document 3] International Publication No. 2014 / 207389

Patent Document 4

Patent Document 5

Patent Document 6

Non-Patent Document

[0010]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0011] Nevertheless, there is still a need to provide polymer latexes that are at least partially based on bio-based monomers and that are suitable as binders in aqueous coating compositions, particularly aqueous coating compositions for external and internal applications, having an acceptable or improved application profile.

Means for Solving the Problems

[0012] Surprisingly, polymer latexes based on a certain amount of monomer M1 selected from cyclopentyl acrylate and cyclopentyl methacrylate, in combination with other conventional or bio-based monomers M2 as defined herein, have been found to improve the coating properties of coating compositions, particularly the gloss, thickening efficiency, diffusion rate (opacity), adhesion to the coated surface, particularly the adhesion of the coating to a surface pre-coated with an alkyd resin (alkyd adhesion). Furthermore, monomer M1 can be obtained from biological sources - at least with respect to their alkanol moieties - thus allowing for a reduction in fossil carbon in the polymer latex.

[0013] The present invention therefore provides an aqueous polymer latex of a film-forming copolymer obtained by aqueous emulsion polymerization of ethylenically unsaturated monomers M, i. from 5 to 70% by weight, in particular from 10 to 60% by weight, of at least one monomer M1 chosen from cyclopentyl acrylate, cyclopentyl methacrylate and mixtures thereof, based on the total amount of monomers M; ii. 20 to 90% by weight, in particular 30 to 80% by weight, of C2-C acrylic acid, excluding tert-butyl acrylate, based on the total amount of monomers M 20 -C5-C alkyl esters and methacrylic acid 20 at least one monomer M2 selected from alkyl esters, as well as mixtures thereof; iii. 0 to 40% by weight, in particular 0 to 35% by weight, of one or more monomers M3 selected from tert-butyl acrylate, C1-C4-alkyl esters of methacrylic acid, cyclohexyl methacrylate, isobornyl methacrylate and monovinyl aromatic monomers, and mixtures thereof, based on the total amount of monomers M; wherein the total amount of monomers M1 and M3 is in the range of 5 to 70% by weight, in particular in the range of 10 to 60% by weight, based on the total amount of ethylenically unsaturated monomers M, and the total amount of monomers M1, M2 and M3 is at least 85% by weight, based on the total amount of ethylenically unsaturated monomers M.

[0014] The present invention also relates to a process for producing the aqueous polymer latex of the present invention, which process comprises carrying out an aqueous emulsion polymerization of monomer M.

[0015] The present invention also relates to the use of these polymer latexes as binders in water-based coating compositions.

[0016] Furthermore, the present invention provides a) a binder polymer in the form of an aqueous polymer latex as defined herein; b) at least one further component conventionally used in water-based coating compositions which is not a binder; The present invention relates to a water-based coating composition comprising:

[0017] The present invention is associated with several advantages. The polymer latex is stable and provides a good and balanced application profile in water-based coating compositions, such as improved thickening efficiency, improved adhesion properties, e.g., high dry alkyd adhesion, improved spreading rate (opacity), high block resistance, good stain release properties, good humidity scrub resistance and low stain build-up. Since the polymer latexes contain significant amounts of the monomers M1, M2 and M3 that can be obtained from bio-renewable resources, at least for the monomer M1, and also for a portion of the monomers M2 and M3, they allow a significant reduction in the need for fossil carbon, in particular by at least 10%, in particular by at least 25%, or even by at least 40%, for example 55%, up to 100%. The incorporation of biocarbon and the reduction of fossil carbon can reduce the carbon footprint of the polymer latex.

[0018] Due to their balanced application profile, polymer latexes are particularly useful as binders in waterborne architectural coatings and have beneficial properties in waterborne primer and waterborne topcoat formulations and in both exterior and interior architectural paints. DETAILED DESCRIPTION OF THE INVENTION

[0019] Here, and throughout this specification, the term "bio-based monomer" means that the respective monomer is at least partially produced from molecules obtained from biorenewable resources, e.g., biomass. Such molecules are characterized by a biocarbon content of at least 90 mol%, preferably at least 95 mol%, e.g., 100 mol%, based on the total amount of carbon atoms in the cyclopentanol.

[0020] The term "biocarbon" indicates that the carbon is of biological origin and comes from biomaterials / renewable resources. Here and below, renewable sources and biorenewable sources are used synonymously and refer to sources of biological origin other than fossil sources. Biocarbon content and biomaterial content are expressions that indicate the same value. Materials of renewable origin or biomaterials are organic materials whose carbon comes from recently fixed CO2 by photosynthesis (at the human scale) from the atmosphere. Biomaterials (carbon of 100% natural origin) are organic materials whose carbon comes from recently fixed CO2 by photosynthesis from the atmosphere (at the human scale). -12 larger, typically about 1.2 x 10 -12 isotope ratio of 14 C / 12 C, but fossil materials have zero ratios. In fact, the isotopes 14 C is formed in the atmosphere and integrated via photosynthesis on timescales up to several decades. 14 The half-life of C is 5,730 years. Therefore, materials derived from photosynthesis, i.e. plants in general, are necessarily isotopic. 14 C. The determination of the content of biomaterials or biocarbons can be carried out in accordance with standards ASTM D 6866-12, method B (ASTM D 6866-06) and ASTM D 7026 (ASTM D 7026-04).

[0021] Here, and throughout this specification, the term "(meth)acrylic" includes both acrylic and methacrylic groups. Thus, the term "(meth)acrylate" includes acrylates and methacrylates, and the term "(meth)acrylamide" includes acrylamides and methacrylamides.

[0022] Here, and throughout this specification, the term "water-based coating composition" means a liquid aqueous coating composition that contains a sufficient amount of water as the continuous phase to achieve flowability.

[0023] Here, and throughout this specification, the terms "wt%" and "% by weight (% bw)" are used interchangeably.

[0024] Here and throughout this specification, the term "pphm" means parts per hundred monomers, i.e. parts by weight per hundred parts of monomer, and corresponds to the relative amount in % by weight of a particular substance based on the total amount of monomers M.

[0025] Herein, and throughout this specification, the term "ethylenically unsaturated monomer" is understood to mean a monomer having at least one C=C double bond, for example 1, 2, 3 or 4 C=C double bonds, which are radically polymerizable, i.e., polymerized under the conditions of an aqueous radical emulsion polymerization process to give a polymer having a backbone of carbon atoms. Herein, and throughout this specification, the term "monoethylenically unsaturated" is understood to mean a monomer having a single C=C double bond and susceptible to radical polymerization under the conditions of aqueous radical emulsion polymerization.

[0026] Here and throughout this specification, the terms "ethoxylated" and "polyethoxylated" are used interchangeably to refer to compounds having oligo- or polyoxyethylene groups formed by the repeating unit O-CH2CH2. In this context, the term "degree of ethoxylation" refers to the number average of the repeating unit O-CH2CH2 in these compounds.

[0027] Here, and throughout this specification, the term "non-ionic" in the context of compounds, particularly monomers, means that the respective compound does not have ionic functional groups or any functional groups that can be converted to ionic groups by protonation or deprotonation.

[0028] The prefix C as used herein and throughout this specification in connection with a compound or molecular moiety n -C m Each indicates the range of possible numbers of carbon atoms that a molecular moiety or compound can have. n The term "alkyl" refers to a group of linear or branched saturated hydrocarbon radicals having 1 to n carbon atoms. n / Cm The term "alkyl" denotes a mixture of two alkyl groups, one having n carbon atoms and the other having m carbon atoms.

[0029] For example, C1-C 20 The term alkyl refers to a group of straight-chain or branched saturated hydrocarbon radicals having from 1 to 20 carbon atoms, the term C1-C4 alkyl refers to a group of straight-chain or branched saturated hydrocarbon radicals having from 1 to 4 carbon atoms, and C5-C 20Alkyl represents a group of straight-chain or branched saturated hydrocarbon radicals having from 5 to 20 carbon atoms. Examples of alkyl include 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, Examples include, but are not limited to, 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, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyldocosyl, and in the case of nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, and heneicosyldocosyl, their isomers, particularly mixtures of isomers, such as "isononyl" and "isodecyl." Examples of C1-C4-alkyl are for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl.

[0030] The term "cyclopentyl," as used herein, refers to a monocyclic alicyclic radical having 5 carbon atoms that is unsubstituted or substituted with 1, 2, 3, or 4 methyl radicals.

[0031] The term "cyclohexyl," as used herein, refers to a monocyclic alicyclic radical having 6 carbon atoms that is unsubstituted or substituted with 1, 2, 3, or 4 methyl radicals.

[0032] The term "isobornyl" refers to 1,7,7 trimethylbicyclo[2.2.1]heptyl.

[0033] According to the invention, the monomers M comprise at least one monomer M1 chosen from cyclopentyl acrylate, cyclopentyl methacrylate, and mixtures thereof.

[0034] In a particular group of embodiments, the monomers M1 comprise at least 50% by weight, in particular at least 80% by weight, in particular at least 90% by weight, of cyclopentyl methacrylate, based on the total amount of the monomers M1. In particular, the monomer M1 is cyclopentyl methacrylate.

[0035] In yet another particular group of embodiments, the monomers M1 are a mixture comprising cyclopentyl acrylate and cyclopentyl methacrylate in an amount of at least 50% by weight, in particular at least 80% by weight, in particular at least 90% by weight, based on the total amount of the monomers M1. In this particular group of embodiments, the monomer molar ratio of cyclopentyl acrylate to cyclopentyl methacrylate is in particular in the range from 1:1 to 10:1.

[0036] Cyclopentyl acrylate and cyclopentyl methacrylate are typically produced by esterification of acrylic acid or methacrylic acid, respectively, with cyclopentanol, or by transesterification of methyl (meth)acrylate or ethyl (meth)acrylate, respectively, with cyclopentanol. Cyclopentyl (meth)acrylate—at least with respect to its alkanol portion—can be obtained from biological sources, thus allowing for a reduction in fossil carbon in the polymer latex.

[0037] Cyclopentanol can be produced from furfural via catalytic hydrogenation, as described in Journal of Energy Chemistry 23 (2014) 91-96. Furfural can be obtained, for example, from biomass. Such cyclopentanol has a biocarbon content of approximately 100 mol%, thus making it possible to produce cyclopentyl methacrylate and cyclopentyl acrylate with biocarbon contents of at least 55 mol% and at least 62 mol%, respectively.

[0038] The acrylic acid and / or methacrylic acid used in the esterification can be obtained from fossil sources according to standard procedures. Acrylic acid can also be prepared from renewable raw materials, for example according to WO 2006 / 092272 or DE 10 2006 039 203 or EP 2 922 580.

[0039] Preferably, at least a portion of the extract used to synthesize M1 is derived from biorenewable raw materials. Accordingly, a particular embodiment of the present invention relates to a polymer latex as defined herein, in which at least the carbon atoms of the cyclopentyl groups in the monomer M1 are of biological origin, i.e., they are at least partially made of biocarbon. In particular, the cyclopentanol used to prepare the monomer M1 preferably has a biocarbon content of at least 90 mol%, based on the total amount of carbon atoms in the cyclopentanol. This content is advantageously higher, in particular 95 mol% or more, preferably 98 mol% or more, and advantageously equal to 100 mol%. Similarly, acrylic acid and / or methacrylic acid may be produced from renewable materials. However, acrylic acid and / or methacrylic acid produced from biomaterials has not been available on a large scale to date. Consequently, the monomer M1 preferably has a biocarbon content of at least 51 mol%, in particular at least 55 mol%, based on the total amount of carbon atoms in the cyclopentyl acrylate and cyclopentyl methacrylate, respectively. By using monomers M1 of at least partial biological origin, the demand for fossil carbon in the polymer latex can be significantly reduced, in particular amounts of carbon of biological origin of at least 10 mol %, in particular at least 15 mol % or at least 20 mol % or more, for example at least 30 mol %, or at least 40 mol %, or at least 50 mol % or more can be achieved.

[0040] The total amount of monomers M1 is from 5 to 70% by weight, in particular from 10 to 60% by weight or from 15 to 60% by weight, in particular from 20 to 50% by weight, based on the total weight of monomers M.

[0041] In addition to the monomers M1, the monomers M forming the polymer of the latex may include one or more monomers M2 as defined above.

[0042] Suitable monomers M2 are -Ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, 2-methylbutyl acrylate, isoamyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, isodecyl acrylate, 2-propylheptyl acrylate, lauryl acrylate, C 12 / C 14 -Alkyl acrylate, C 12 -C 15 -Alkyl acrylate, isotridecyl acrylate, C 17 -Alkyl acrylate, C 16 / C 18 -C2-C of acrylic acid, excluding tert-butyl acrylate, including but not limited to alkyl acrylates and stearyl acrylate 20 alkyl esters, -n-Butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, n-decyl methacrylate, 2-propylheptyl methacrylate, lauryl methacrylate, C 12 / C 14 -Alkyl methacrylate, C 12 -C 15 -Alkyl methacrylate, isotridecyl methacrylate, C 16 / C 18 C5-C of methacrylic acid, including but not limited to alkyl methacrylate and stearyl methacrylate 20 alkyl esters, and -A mixture of them is selected from the group consisting of:

[0043] Preferred monomers M2 are selected from the group consisting of ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, 2-methylbutyl acrylate, isoamyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-octyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate, and mixtures thereof. Preferably, monomer M2 comprises at least one of n-butyl acrylate, 2-ethylhexyl acrylate, 2-octyl acrylate, isoamyl acrylate (=3-methylbutyl acrylate), 2-methylbutyl acrylate, and isobutyl acrylate, or mixtures thereof. Isoamyl acrylate, 2-methylbutyl acrylate, or isobutyl acrylate may be produced from fossil sources or may be at least partially bio-based. In particular, the isoamyl, 2-methylbutyl, and isobutyl portions of isoamyl acrylate, 2-methylbutyl acrylate, and isobutyl acrylate, respectively, are biobased, i.e., the monomers are obtained from the esterification of acrylic acid, which may be biobased or fossil-derived, with biobased isoamyl alcohol, 2-methylbutanol, or isobutanol, respectively. Similarly, the 2-octanol portion of 2-octyl acrylate may be biobased, i.e., the monomers are obtained from the esterification of acrylic acid, which may be biobased or fossil-derived, with biobased 2-octanol.

[0044] In a preferred group of embodiments, the monomer M2 comprises isobutyl acrylate, in particular bio-based isobutyl acrylate. In particular, the monomer is isobutyl acrylate, in particular bio-based isobutyl acrylate. In this preferred group of embodiments, the monomer M2 also comprises isobutyl acrylate and at least one further C2-C acrylate different from isobutyl acrylate. 10 It may also be a mixture with alkyl acrylates, such as n-butyl acrylate, isoamyl acrylate, 2-methylbutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate.

[0045] In the context of this group of embodiments, the amount of isobutyl acrylate is preferably in the range of 20 to 80% by weight, in particular 25 to 75% by weight, in particular 30 to 70% by weight, based on the total amount of monomers M.

[0046] In another preferred group of embodiments, the monomer M2 comprises n-butyl acrylate. In this group of embodiments, n-butyl acrylate may be the only monomer, or n-butyl acrylate may be present in combination with at least one further C2-C2 monomer different from n-butyl acrylate. 10 It may also be a mixture with alkyl acrylates, such as isoamyl acrylate, 2-methylbutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate.

[0047] In the context of this group of embodiments, the amount of n-butyl acrylate is preferably in the range of 20 to 80% by weight, in particular 25 to 75% by weight, in particular 30 to 70% by weight, based on the total amount of monomers M.

[0048] Isobutyl acrylate, 2-methylbutyl acrylate, isopentyl acrylate and 2-octyl acrylate are typically prepared by esterification of acrylic acid with isobutanol (2-methylpropan-1-ol), 2-methylbutanol, isopentanol (3-methylbutan-1-ol) or 2-octanol, or by transesterification of methyl acrylate or ethyl acrylate with isobutanol (2-methylpropan-1-ol), 2-methylbutan-1-ol, isopentanol (3-methylbutan-1-ol) or 2-octanol, respectively.

[0049] Isobutanol, 2-methylbutanol, and isopentanol, as well as mixtures thereof, can be produced on a large scale by fermentation from a variety of renewable feedstocks, including corn, wheat, sorghum, barley, and sugarcane, particularly from cellulose-containing feedstocks, thus each from biological or renewable sources. In particular, fermentation can produce mixtures containing different alkanols, from which isobutanol, 2-methylbutan-1-ol, and 3-methylbutan-1-ol can be separated by conventional techniques, such as fractional distillation. This can result in pure alcohols (greater than 90% pure) or mixtures containing at least two alcohols selected from the group consisting of isobutanol, 2-methylbutan-1-ol, and 3-methylbutan-1-ol in a total amount of at least 80%, particularly at least 90%. 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-methylbutan-1-ol may vary, for example, from 1:10 to 10:1, and is particularly in the range of 1:1 to 10:1. 2-Octanol can be produced by alkaline-catalyzed thermal cleavage of ricinoleic acid, with sebacic acid as a by-product. Castor oil, which is primarily composed of ricinoleic acid, is the primary feedstock. Therefore, the inclusion of these monomers M2 in a polymer latex significantly increases the amount of biocarbon in the polymer latex. The incorporation of biocarbon and the reduction of fossil carbon can reduce the carbon footprint of the polymer latex.

[0050] Thus, a specific embodiment of the present invention relates to a polymer latex as defined herein, in which at least the carbon atoms of the isobutyl, 2-methylbutyl, isoamyl, and 2-octyl groups in the monomer M2, particularly the carbon atoms of the isobutyl groups in the monomer M2, are of biological origin, i.e., are at least partially made of biocarbon. In particular, the isobutanol, 2-methylbutan-1-ol, 3-methylbutanol, and 2-octanol used to prepare the monomer M2 preferably have a biocarbon content of at least 90 mol % based on the total amount of carbon atoms in the isobutanol, 2-methylpentanol, 3-methylbutanol, and 2-octanol, respectively. This content is advantageously higher, particularly 95 mol % or more, preferably 98 mol % or more, and advantageously equal to 100 mol %. Similarly, acrylic acid may be produced from renewable materials. However, acrylic acid produced from biomaterials has not been available on a large scale until now. As a result, the monomer M2 preferably has a biocarbon 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, isopentyl acrylate, and 2-octyl acrylate, respectively. By using a monomer M2 of at least partial biological origin, the demand for fossil carbon in the polymer latex can be significantly reduced. In particular, amounts of biologically-sourced carbon of at least 10 mol%, particularly at least 15 mol%, or at least 20 mol%, for example 30 mol% or 40 mol% or more can be achieved.

[0051] The total amount of monomers M2 is from 20 to 90% by weight, in particular from 30 to 80% by weight or from 30 to 70% by weight, in particular from 40 to 65% by weight, based on the total weight of monomers M.

[0052] In addition to the monomers M1 and M2, the monomers M forming the polymer of the latex may also include one or more monomers M3 as defined above.

[0053] Suitable monomers M3 are C1-C4-Alkyl esters of methacrylic acid, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, isobutyl methacrylate and tert-butyl methacrylate, tert-butyl acrylate, -cyclohexyl methacrylate, isobornyl methacrylate, monovinyl aromatic monomers, such as styrene, 2-methylstyrene, 4-methylstyrene, and - their mixtures, is selected from the group consisting of:

[0054] In a preferred group of embodiments, the monomer M3 is C1-C4-alkyl esters of methacrylic acid, in particular methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and tert-butyl methacrylate, tert-butyl acrylate, -cyclohexyl methacrylate, isobornyl methacrylate, styrene, and - their mixtures, is selected from the group consisting of:

[0055] In this group, the monomers M3 are in particular -methyl methacrylate, n-butyl methacrylate, tert-butyl acrylate, -cyclohexyl methacrylate, isobornyl methacrylate, styrene, and - their mixtures, is selected from the group consisting of:

[0056] In a particular group of embodiments (M3-A), the monomer M3 comprises methyl methacrylate in an amount of at least 50% by weight, in particular at least 80% by weight or 100% by weight, based on the total amount of monomers M3 in the monomers M. In this group, more particularly, the monomer M3 is selected from the group consisting of methyl methacrylate and combinations of methyl methacrylate with n-butyl methacrylate, tert-butyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate or styrene.

[0057] In this particular group of embodiments M3-A, the monomer M3 which is methyl methacrylate is preferred.

[0058] In the context of the embodiment group M3-A, the amount of methyl methacrylate is preferably in the range from 1 to 40% by weight, in particular from 1.5 to 35% by weight, in particular from 2 to 30% by weight, based on the total amount of monomers M.

[0059] In another particular group of embodiments (M3-B), the monomers M3 comprise styrene in an amount of at least 50% by weight, in particular at least 80% by weight or 100% by weight, based on the total amount of monomers M3 in the monomers M. In this group, more particularly, the monomers M3 are selected from the group consisting of styrene and combinations of styrene with methyl methacrylate, n-butyl methacrylate, tert-butyl acrylate, cyclohexyl methacrylate or isobornyl methacrylate.

[0060] In this particular group of embodiments M3-A, the monomer M3 which is methyl methacrylate is preferred.

[0061] In the context of the embodiment group M3-B, the amount of styrene is preferably in the range from 1 to 30% by weight, in particular from 1.5 to 25% by weight, in particular from 2 to 20% by weight, based on the total amount of monomers M.

[0062] The total amount of monomers M3 is from 0 to 40% by weight, in particular from 0 to 35% by weight or from 1 to 35% by weight, based on the total weight of monomers M.

[0063] The total amount of monomers M1 and M3, based on the total amount of ethylenically unsaturated monomers M, is preferably in the range from 5 to 70% by weight, in particular in the range from 10 to 65% by weight, in particular in the range from 15 to 60% by weight.

[0064] The total amount of monomers M1, M2 and M3, based on the total amount of ethylenically unsaturated monomers M, is at least 85% by weight, in particular at least 90% by weight, in particular at least 95% by weight.

[0065] The weight ratio of M1 to M2 is generally in the range of 1:10 to 10:1, in particular in the range of 1:5 to 5:1, preferably in the range of 1:4 to 4:1, in particular in the range of 1:3 to 3:1.

[0066] When M3 is present, the weight ratio of M1 to M3 is generally in the range of from 1:5 to 30:1, in particular in the range of from 1:4 to 25:1, preferably in the range of from 1:2 to 20:1.

[0067] The monomers M may further comprise at least one monomer M4 selected from monoethylenically unsaturated monomers having an acidic group.

[0068] Suitable monomers M4 include: monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, such as acrylic acid, methacrylic acid, crotonic acid, 2-ethylpropenoic acid, 2-propylpropenoic acid, 2-acryloxyacetic acid and 2-methacryloxyacetic acid, monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms, such as itaconic acid, citraconic acid, maleic acid and fumaric acid, - semiesters of monoethylenically unsaturated dicarboxylic acids having 4 to 6 carbon atoms with C1-C4 alkanols, for example methanol or ethanol, for example the semiesters of itaconic acid, citraconic acid, maleic acid or fumaric acid with methanol or ethanol, monoethylenically unsaturated sulfonic acids, such as vinylsulfonic acid, allylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, monoethylenically unsaturated phosphonic acids, such as vinylphosphonic acid, allylphosphonic acid, styrenephosphonic acid and 2-acrylamido-2-methylpropanephosphonic acid, monoethylenically unsaturated phosphoric acids, such as monophosphates of hydroxyalkyl acrylates, monophosphates of hydroxyalkyl methacrylates, monophosphates of alkoxylated hydroxyalkyl acrylates and monophosphates of alkoxylated hydroxyalkyl methacrylates, in particular 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 These include, but are not limited to:

[0069] The aforementioned monomers M4 can be present in their acid form or in the form of their salts, in particular in the form of their alkali metal or ammonium salts.

[0070] Among the above-mentioned monomers M4, monoethylenically unsaturated monocarboxylic acids, monoethylenically unsaturated dicarboxylic acids, and monoethylenically unsaturated sulfonic acids, as well as their salts, particularly alkali metal salts and ammonium salts, are preferred. Acrylic acid, methacrylic acid, itaconic acid, 2-acrylamido-2-methylpropanesulfonic acid, and their salts, particularly alkali metal salts and ammonium salts, as well as combinations thereof, are particularly preferred. Monoethylenically unsaturated monocarboxylic acids and monoethylenically unsaturated sulfonic acids, as well as their salts, particularly alkali metal salts and ammonium salts, are more preferred, particularly acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, their salts, particularly alkali metal salts and ammonium salts, as well as mixtures of the aforementioned monomers. In a specific group of embodiments, monomer M4 comprises methacrylic acid. In particular, monomer M4 is methacrylic acid or a mixture of acrylic acid and methacrylic acid. In another specific group of embodiments, monomer M4 comprises acrylic acid. In another particular group of embodiments, the monomer M4 comprises 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof, in particular an alkali metal or ammonium salt. In particular, the monomer M4 is 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof, in particular an alkali metal or ammonium salt, or a mixture of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof, in particular an alkali metal or ammonium salt.

[0071] The total amount of monomers M4 is 0.05 to 5% by weight or 0.1 to 4% by weight, in particular 0.05 to 3.5% by weight or 0.1 to 3% by weight, in particular 0.2 to 3% by weight or 0.5 to 3% by weight or 0.5 to 2% by weight, based on the total weight of monomers M.

[0072] The monomers M may further comprise at least one monoethylenically unsaturated nonionic monomer M5 having a solubility in deionized water of at least 60 g / L at 20° C. and 1 bar.

[0073] Suitable monomers M5 are selected from the group consisting of nonionic monoethylenically unsaturated monomers having functional groups selected from the group consisting of hydroxyalkyl groups, in particular hydroxy-C2-C4-alkyl groups, primary carboxamide groups, urea groups, keto groups and combinations thereof.

[0074] The total amount of monomers M5 usually does not exceed 10% by weight, in particular 7% by weight, based on the total amount of monomers M. In particular, the total amount of monomers M5 is usually from 0 to 9.95% by weight, and if present, from 0.05 to 9.95% by weight, in particular from 0.1 to 7% by weight, in particular from 0.1 to 5% by weight or from 0.1 to 4% by weight or from 0.5 to 3% by weight or from 1 to 3% by weight, based on the total weight of monomers M.

[0075] Examples of monomer M5 having a carboxamide group (hereinafter referred to as monomer M5a) include, but are not limited to, primary amides of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, such as acrylamide and methacrylamide, and C1-C4-alkylamides of monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, such as N-methylacrylamide, 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 acrylamides and methacrylamides.

[0076] Examples of monomers M5 having a urea group (hereinafter referred to as monomers M5b) are C1-C4-alkyl esters of acrylic or methacrylic acid and N-C1-C4-alkylamides of acrylic or methacrylic acid, in which the C1-C4-alkyl group is a urea group or a 2-oxoimidazoline group, such as 2-(2-oxo-imidazolidin-1-yl)ethyl acrylate, 2-(2-oxo-imidazolidin-1-yl)ethyl methacrylate (respectively 2-ureidoacrylate and 2-ureido). N-(2-acryloxyethyl)urea, N-(2-methacryloxyethyl)urea, N-(2-oxo-imidazolidin-1-yl)ethyl)acrylamide, N-(2-(2-oxo-imidazolidin-1-yl)ethyl)methacrylamide, and allyl- or vinyl-substituted urea and allyl- or vinyl-substituted 2-oxoimidazoline compounds, such as 1-allyl-2-oxoimidazoline, N-allyl urea, and N-vinyl urea.

[0077] Examples of the monomer M5 having a keto group (hereinafter referred to as monomer M5c) are: C2-C8-oxoalkyl esters of acrylic or methacrylic acid and N-C2-C8-oxoalkylamides of acrylic or methacrylic acid, such as diacetoneacrylamide (DAAM) and diacetonemethacrylamide, and C1-C4-alkyl esters of acrylic or methacrylic acid and N-C1-C4-alkylamides of acrylic or methacrylic acid, in which the C1-C4-alkyl group has a 2-acetylacetoxy group of the formula O-C(=O)-CH2-C(=O)-CH3 (also called acetoacetoxy group), such as acetoacetoxyethyl acrylate, acetoacetoxypropyl methacrylate, acetoacetoacetoxybutyl methacrylate and 2-(acetoacetoacetoxy)ethyl methacrylate.

[0078] Preferably, the monomer M is i. 5 to 70% by weight, in particular 10 to 65% by weight or 15 to 60% by weight, in particular 20 to 50% by weight, of cyclopentyl methacrylate as monomers M1, based on the total amount of monomers M; ii. 20 to 90% by weight, in particular 30 to 80% by weight or 30 to 70% by weight, in particular 40 to 65% by weight, of at least one monomer M2 comprising or being isobutyl acrylate, based on the total amount of monomers M; iii. 0 to 40% by weight, in particular 0 to 35% by weight or 1 to 35% by weight, of at least one monomer M3 comprising or selected from the group consisting of methyl methacrylate, styrene or combinations thereof, based on the total amount of monomers M; iv. 0.05 to 5% by weight or 0.1 to 4% by weight, in particular 0.05 to 3.5% by weight or 0.1 to 3% by weight, in particular 0.2 to 3% by weight or 0.5 to 3% by weight or 0.5 to 2% by weight, based on the total amount of monomers M, of one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having an acidic group, v. if present, from 0 to 9.95 wt.-%, from 0.05 to 9.95 wt.-%, in particular from 0.1 to 7 wt.-%, in particular from 0.1 to 5 wt.-% or from 0.1 to 4 wt.-% or from 0.5 to 3 wt.-% or from 1 to 3 wt.-%, based on the total weight of the monomers M, of one or more non-ionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20°C and 1 bar, or, i. 5 to 70% by weight, in particular 10 to 65% by weight or 15 to 60% by weight, in particular 20 to 50% by weight, of cyclopentyl methacrylate as monomers M1, based on the total amount of monomers M; ii. 20 to 90% by weight, in particular 30 to 80% by weight or 30 to 70% by weight, in particular 40 to 65% by weight, of at least one monomer M2 comprising or being n-butyl acrylate, based on the total amount of monomers M, iii. 0 to 40% by weight, in particular 0 to 35% by weight or 1 to 35% by weight, of at least one monomer M3 comprising or selected from the group consisting of methyl methacrylate, styrene or combinations thereof, based on the total amount of monomers M; iv. 0.05 to 5% by weight or 0.1 to 4% by weight, in particular 0.05 to 3.5% by weight or 0.1 to 3% by weight, in particular 0.2 to 3% by weight or 0.5 to 3% by weight or 0.5 to 2% by weight, based on the total amount of monomers M, of one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having an acidic group, v. if present, from 0 to 9.95 wt.-%, from 0.05 to 9.95 wt.-%, in particular from 0.1 to 7 wt.-%, in particular from 0.1 to 5 wt.-% or from 0.1 to 4 wt.-% or from 0.5 to 3 wt.-% or from 1 to 3 wt.-%, based on the total weight of the monomers M, of one or more non-ionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20°C and 1 bar, wherein the total amount of monomers M1 and M3 is in the range of 5 to 70% by weight, in particular in the range of 10 to 65% by weight, in particular in the range of 15 to 60% by weight, based on the total amount of ethylenically unsaturated monomers M, and the total amount of monomers M1, M2 and M3 is at least 85% by weight, in particular at least 90% by weight, in particular at least 95% by weight, based on the total amount of ethylenically unsaturated monomers M.

[0079] In one particular group of embodiments, the monomer M is i. from 15 to 69.95% by weight, in particular from 20 to 64.8% by weight, in particular from 25 to 59.4% by weight, of cyclopentyl methacrylate as monomer M1, based on the total amount of monomers M; ii. from 30 to 84.95% by weight, in particular from 35 to 79.8% by weight, in particular from 40 to 74.4% by weight, of isobutyl acrylate as monomer M2, based on the total amount of monomers M; iii. 0.05 to 5% by weight, in particular 0.1 to 4% by weight, in particular 0.5 to 3% by weight, of one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having an acidic group, based on the total amount of monomers M, iv. 0 to 9.95% by weight, in particular 0.05 to 5% by weight, in particular 0.1 to 4% by weight, of one or more non-ionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20° C. and 1 bar, based on the total weight of the monomers M; the total amount of monomers M1 and M2 is at least 85% by weight, in particular at least 90% by weight, in particular at least 95% by weight, based on the total amount of ethylenically unsaturated monomers M, or, i. from 10 to 68.95% by weight, in particular from 15 to 63.4% by weight, in particular from 15 to 57.4% by weight, of cyclopentyl methacrylate as monomer M1, based on the total amount of monomers M; ii. 30 to 70% by weight, in particular 35 to 65% by weight, in particular 40 to 60% by weight, of isobutyl acrylate as monomer M2, based on the total amount of monomers M; iii. 1 to 35% by weight, in particular 1.5 to 30% by weight, in particular 2 to 25% by weight, of monomers M3 selected from methyl methacrylate, styrene and combinations thereof, based on the total amount of monomers M; iv. 0.05 to 5% by weight, in particular 0.1 to 4% by weight, in particular 0.5 to 3% by weight, of one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having an acidic group, based on the total amount of monomers M, v. 0 to 9.95% by weight, in particular 0.05 to 5% by weight, in particular 0.1 to 4% by weight, of one or more non-ionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20° C. and 1 bar, based on the total weight of the monomers M; the total amount of monomers M1 and M3 is in the range of 5 to 70% by weight, in particular in the range of 10 to 65% by weight, in particular in the range of 15 to 60% by weight, based on the total amount of ethylenically unsaturated monomers M, and the total amount of monomers M1, M2 and M3 is at least 85% by weight, in particular at least 90% by weight, in particular at least 95% by weight, based on the total amount of ethylenically unsaturated monomers M, or, i. from 10 to 68.95% by weight, in particular from 15 to 63.4% by weight, in particular from 15 to 57.4% by weight, of cyclopentyl methacrylate as monomer M1, based on the total amount of monomers M; ii. 30 to 70% by weight, in particular 35 to 65% by weight, in particular 40 to 60% by weight, of isobutyl acrylate and at least one C2-C acrylate other than isobutyl acrylate, based on the total amount of monomers M. 10 monomers M2 which are mixtures of alkyl acrylates, for example n-butyl acrylate, isoamyl acrylate, 2-methylbutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate, iii. 1 to 35% by weight, in particular 1.5 to 30% by weight, in particular 2 to 25% by weight, of monomers M3 selected from methyl methacrylate, styrene and combinations thereof, based on the total amount of monomers M; iv. 0.05 to 5% by weight, in particular 0.1 to 4% by weight, in particular 0.5 to 3% by weight, of one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having an acidic group, based on the total amount of monomers M; v. 0 to 9.95% by weight, in particular 0.05 to 5% by weight, in particular 0.1 to 4% by weight, of one or more non-ionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20° C. and 1 bar, based on the total weight of the monomers M; the total amount of monomers M1 and M3 is in the range of 5 to 70% by weight, in particular in the range of 10 to 65% by weight, in particular in the range of 15 to 60% by weight, based on the total amount of ethylenically unsaturated monomers M, and the total amount of monomers M1, M2 and M3 is at least 85% by weight, in particular at least 90% by weight, in particular at least 95% by weight, based on the total amount of ethylenically unsaturated monomers M, or, i. from 10 to 68.95% by weight, in particular from 15 to 63.4% by weight, in particular from 15 to 57.4% by weight, of cyclopentyl methacrylate as monomer M1, based on the total amount of monomers M; ii. 30 to 70% by weight, in particular 35 to 65% by weight, in particular 40 to 60% by weight, of n-butyl acrylate or n-butyl acrylate and at least one C2-C acrylate other than n-butyl acrylate, based on the total amount of monomers M. 10 Monomers M2 which are mixtures of alkyl acrylates, for example isoamyl acrylate, 2-methylbutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate, iii. 1 to 35% by weight, in particular 1.5 to 30% by weight, in particular 2 to 25% by weight, of monomers M3 selected from methyl methacrylate, styrene and combinations thereof, based on the total amount of monomers M; iv. 0.05 to 5% by weight, in particular 0.1 to 4% by weight, in particular 0.5 to 3% by weight, of one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having an acidic group, based on the total amount of monomers M; v. 0 to 9.95% by weight, in particular 0.05 to 5% by weight, in particular 0.1 to 4% by weight, of one or more non-ionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20° C. and 1 bar, based on the total weight of the monomers M; wherein the total amount of monomers M1 and M3 is in the range of 5 to 70% by weight, in particular in the range of 10 to 65% by weight, in particular in the range of 15 to 60% by weight, based on the total amount of ethylenically unsaturated monomers M, and the total amount of monomers M1, M2 and M3 is at least 85% by weight, in particular at least 90% by weight, in particular at least 95% by weight, based on the total amount of ethylenically unsaturated monomers M.

[0080] In a particular group 1 of embodiments, the monomers M are preferably (group 1a of embodiments): i. cyclopentyl methacrylate as monomer M1, in which at least 15 to 69.95% by weight, in particular 20 to 64.8% by weight, in particular 25 to 59.4% by weight, of the carbon atoms of the cyclopentyl groups in the cyclopentyl methacrylate are of biological origin, based on the total amount of monomers M, in particular the biocarbon content of the cyclopentyl methacrylate is at least 51 mol %, in particular at least 55 mol %; ii. isobutyl acrylate as monomer M2, in which at least 30 to 84.95% by weight, in particular 35 to 79.8% by weight, in particular 40 to 74.4% by weight, of the carbon atoms of the isobutyl groups in the isobutyl acrylate are of biological origin, based on the total amount of monomers M, and in particular the biocarbon content of the isobutyl methacrylate is at least 54 mol %, in particular at least 57 mol %, iii. 0.05 to 5% by weight, in particular 0.1 to 4% by weight, in particular 0.5 to 3% by weight, of one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having an acidic group, based on the total amount of monomers M, iv. 0 to 9.95% by weight, in particular 0.05 to 5% by weight, in particular 0.1 to 4% by weight, of one or more non-ionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20° C. and 1 bar, based on the total weight of the monomers M; the total amount of monomers M1 and M2 is at least 85% by weight, in particular at least 90% by weight, in particular at least 95% by weight, based on the total amount of ethylenically unsaturated monomers M, or, i. cyclopentyl methacrylate as monomer M1, in which at least 10 to 68.95% by weight, in particular 15 to 63.4% by weight, in particular 15 to 57.4% by weight, of the carbon atoms of the cyclopentyl groups in the cyclopentyl methacrylate are of biological origin, based on the total amount of monomers M, in particular the biocarbon content of the cyclopentyl methacrylate is at least 51 mol %, in particular at least 55 mol %; ii. isobutyl acrylate as monomer M2, in which at least 30 to 70% by weight, in particular 35 to 65% by weight, in particular 40 to 60% by weight, of the carbon atoms of the isobutyl groups in the isobutyl acrylate are of biological origin, based on the total amount of monomers M, and in particular the biocarbon content of the isobutyl methacrylate is at least 54 mol %, in particular at least 57 mol %, iii. 1 to 35% by weight, in particular 1.5 to 30% by weight, in particular 2 to 25% by weight, of monomers M3 selected from methyl methacrylate, styrene and combinations thereof, based on the total amount of monomers M; iv. 0.05 to 5% by weight, in particular 0.1 to 4% by weight, in particular 0.5 to 3% by weight, of one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having an acidic group, based on the total amount of monomers M, v. 0 to 9.95% by weight, in particular 0.05 to 5% by weight, in particular 0.1 to 4% by weight, of one or more non-ionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20° C. and 1 bar, based on the total weight of the monomers M; the total amount of monomers M1 and M3 is in the range of 5 to 70% by weight, in particular in the range of 10 to 65% by weight, in particular in the range of 15 to 60% by weight, based on the total amount of ethylenically unsaturated monomers M, and the total amount of monomers M1, M2 and M3 is at least 85% by weight, in particular at least 90% by weight, in particular at least 95% by weight, based on the total amount of ethylenically unsaturated monomers M, or, i. cyclopentyl methacrylate as monomer M1, in which at least 10 to 68.95% by weight, in particular 15 to 63.4% by weight, in particular 15 to 57.4% by weight, of the carbon atoms of the cyclopentyl groups in the cyclopentyl methacrylate are of biological origin, based on the total amount of monomers M, in particular the biocarbon content of the cyclopentyl methacrylate is at least 51 mol %, in particular at least 55 mol %; ii. 30 to 70% by weight, in particular 35 to 65% by weight, in particular 40 to 60% by weight, of isobutyl acrylate and at least one C2-C acrylate other than isobutyl acrylate, based on the total amount of monomers M. 10 monomers M2, which are mixtures with alkyl acrylates, such as n-butyl acrylate, isoamyl acrylate, 2-methylbutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate, in which at least the carbon atoms of the isobutyl group in the isobutyl acrylate are of biological origin, and in particular the isobutyl methacrylate has a biocarbon content of at least 54 mol %, in particular at least 57 mol %; iii. 1 to 35% by weight, in particular 1.5 to 30% by weight, in particular 2 to 25% by weight, of monomers M3 selected from methyl methacrylate, styrene and combinations thereof, based on the total amount of monomers M; iv. 0.05 to 5% by weight, in particular 0.1 to 4% by weight, in particular 0.5 to 3% by weight, of one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having an acidic group, based on the total amount of monomers M, v. 0 to 9.95% by weight, in particular 0.05 to 5% by weight, in particular 0.1 to 4% by weight, of one or more non-ionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20° C. and 1 bar, based on the total weight of the monomers M; the total amount of monomers M1 and M3 is in the range of 5 to 70% by weight, in particular in the range of 10 to 65% by weight, in particular in the range of 15 to 60% by weight, based on the total amount of ethylenically unsaturated monomers M, and the total amount of monomers M1, M2 and M3 is at least 85% by weight, in particular at least 90% by weight, in particular at least 95% by weight, based on the total amount of ethylenically unsaturated monomers M, or, i. cyclopentyl methacrylate as monomer M1, in which at least 10 to 68.95% by weight, in particular 15 to 63.4% by weight, in particular 15 to 57.4% by weight, of the carbon atoms of the cyclopentyl groups in the cyclopentyl methacrylate are of biological origin, based on the total amount of monomers M, in particular the biocarbon content of the cyclopentyl methacrylate is at least 51 mol %, in particular at least 55 mol %; ii. 30 to 70% by weight, in particular 35 to 65% by weight, in particular 40 to 60% by weight, of n-butyl acrylate or n-butyl acrylate and at least one C2-C acrylate other than n-butyl acrylate, based on the total amount of monomers M. 10 Monomers M2 which are mixtures of alkyl acrylates, for example isoamyl acrylate, 2-methylbutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate, iii. 1 to 35% by weight, in particular 1.5 to 30% by weight, in particular 2 to 25% by weight, of monomers M3 selected from methyl methacrylate, styrene and combinations thereof, based on the total amount of monomers M; iv. 0.05 to 5% by weight, in particular 0.1 to 4% by weight, in particular 0.5 to 3% by weight, of one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having an acidic group, based on the total amount of monomers M, v. 0 to 9.95% by weight, in particular 0.05 to 5% by weight, in particular 0.1 to 4% by weight, of one or more non-ionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20° C. and 1 bar, based on the total weight of the monomers M; wherein the total amount of monomers M1 and M3 is in the range of 5 to 70% by weight, in particular in the range of 10 to 65% by weight, in particular in the range of 15 to 60% by weight, based on the total amount of ethylenically unsaturated monomers M, and the total amount of monomers M1, M2 and M3 is at least 85% by weight, in particular at least 90% by weight, in particular at least 95% by weight, based on the total amount of ethylenically unsaturated monomers M.

[0081] In particular group 2 of embodiments, the types and amounts of monomers M1, M2, M3, M4 and, if present, M5 are as defined for particular group 1 of embodiments, except that monomer M1 is a mixture of cyclopentyl acrylate and cyclopentyl methacrylate instead of cyclopentyl methacrylate.

[0082] Of the particular group of embodiments 2, embodiment 2a is preferred, in which the types and amounts of the monomers M1, M2, M3, M4 and, if present, M5 are as defined for particular group of embodiments 1a, except that the monomers M1 are a mixture comprising at least 50% by weight, in particular at least 80% by weight, in particular at least 90% by weight, of cyclopentyl acrylate and cyclopentyl methacrylate instead of cyclopentyl methacrylate, based on the total amount of monomers M1.

[0083] In addition to the aforementioned monomers M1, M2, M3, M4 and M5, the monomers M may comprise one or more further monomers different from the aforementioned monomers M. Suitable monomers M different from the monomers M1, M2, M3, M4 and M5 include: monomers M6 chosen from monoethylenically unsaturated nonionic monomers having a silane function or an epoxy group, monomers M7 chosen from multiethylenically unsaturated monomers, i.e. monomers having at least two non-conjugated ethylenically unsaturated double bonds, monomers M8 selected from monoethylenically unsaturated copolymerizable UV initiators, These include, but are not limited to:

[0084] Suitable monomers M6 include monoethylenically unsaturated silane-functional monomers (monomers M6a), such as monomers having at least one mono-, di-, and / or tri-C1-C4-alkoxysilane group in addition to an ethylenically 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, based on the total amount of ethylenically unsaturated monomers M, is usually no more than 1% by weight, often in the range of 0.01 to 1% by weight, preferably in the range of 0.05 to 0.7% by weight.

[0085] Suitable monomers M6 also include monoethylenically unsaturated monomers having at least one epoxy group (monomers M6b), in particular glycidyl groups, such as glycidyl acrylate, glycidyl methacrylate, 2-glycidyloxyethyl acrylate and 2-glycidyloxyethyl methacrylate. The amount of monomers M6b, if present, will usually not exceed 2% by weight, often ranging from 0.01 to 2% by weight, preferably from 0.05 to 1% by weight, based on the total amount of ethylenically unsaturated monomers M.

[0086] The monomers M may also comprise multiethylenically unsaturated monomers (monomers M7), i.e. monomers having at least two non-conjugated ethylenically unsaturated double bonds, the amount of said monomers M7 generally not exceeding 1% by weight, often ranging from 0 to 1% by weight, in particular from 0 to 0.5% by weight, based on the total amount of ethylenically unsaturated monomers M.

[0087] Examples of multiethylenically unsaturated monomers M7 include: diesters of monoethylenically unsaturated C3-C6 monocarboxylic acids with saturated aliphatic or cycloaliphatic diols, in particular diesters of acrylic or methacrylic acid, such as the diacrylates and dimethacrylates of ethylene glycol (1,2-ethanediol), propylene glycol (1,2-propanediol), 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol (2,2-dimethyl-1,3-propanediol), 1,6-hexanediol and 1,2-cyclohexanediol, monoesters of monoethylenically unsaturated C3-C6 monocarboxylic acids with monoethylenically unsaturated aliphatic or alicyclic monohydroxy compounds, such as the acrylates and methacrylates of vinyl alcohol (ethenol), allyl alcohol (2-propen-1-ol), 2-cyclohexen-1-ol or norbornenol, such as allyl acrylate and allyl methacrylate, and Divinyl aromatic compounds, such as 1,3-divinylbenzene, 1,4-divinylbenzene Examples include:

[0088] Polymerized monoethylenically unsaturated copolymerizable UV initiator M8 causes crosslinking of polymer chains when exposed to sunlight. Monomer M8 has an ethylenically unsaturated double bond, particularly an acrylate or methacrylate group, and a moiety that decomposes under UV irradiation to form a radical. Such groups are typically benzophenone, acetophenone, benzoin, or carbonate groups attached to a phenyl ring. Such compounds are disclosed, for example, in EP 346734, EP 377199, DE 4037079, DE 3844444, EP 1213, and U.S. Patent Application Publication No. 2015 / 0152297. Examples include 4-acryloxybenzophenone (=4-benzoylphenylpropenoate), 4-methacryloxybenzophenone (=4-benzoylphenyl 2-methylpropenoate), 4-(2-acryloxyethoxy)benzophenone (=2-(4-benzoylphenoxy)ethylpropenoate), 4-(2-methacryloxyethoxy)benzophenone (=2-(4-benzoylphenoxy)ethyl 2-methyl-propenoate), O-(2-(meth)acryloxyethyl)-O-(benzoylphenyl)carbonate, and O-(2-(meth)acryloxyethyl)-O-(acetylphenyl)carbonate The amount of said monomer M8 generally does not exceed 1% by weight, and when present, is typically in the range of 0.01 to 1% by weight, in particular 0.02 to 0.5% by weight, based on the total amount of ethylenically unsaturated monomers M.

[0089] In particular, the monomer M is (group 3 of embodiments): i. cyclopentyl methacrylate as monomer M1, in which at least 15 to 69.95% by weight, in particular 20 to 64.8% by weight, in particular 25 to 59.4% by weight, of the carbon atoms of the cyclopentyl groups in the cyclopentyl methacrylate are of biological origin, based on the total amount of monomers M, in particular the biocarbon content of the cyclopentyl methacrylate is at least 51 mol %, in particular at least 55 mol %; ii. isobutyl acrylate as monomer M2, in which at least 30 to 84.95% by weight, in particular 35 to 79.8% by weight, in particular 40 to 74.4% by weight, of the carbon atoms of the isobutyl groups in the isobutyl acrylate are of biological origin, based on the total amount of monomers M, and in particular the biocarbon content of the isobutyl methacrylate is at least 54 mol %, in particular at least 57 mol %, iii. 0.05 to 5 wt. %, in particular 0.1 to 4 wt. %, in particular 0.5 to 3 wt. % of one or more monoethylenically unsaturated monomers M4 selected from acrylic acid, methacrylic acid, itaconic acid and combinations thereof, based on the total amount of monomers M; iv. 0 to 9.95 wt. %, in particular 0.05 to 5 wt. %, in particular 0.1 to 4 wt. %, based on the total weight of the monomers M, of one or more nonionic monomers M5 having a solubility in deionized water at 20° C. and 1 bar of at least 60 g / L and having functional groups selected from the group consisting of hydroxyalkyl groups, primary carboxamide groups, urea groups, keto groups, and combinations thereof; and v. 0 to 1% by weight, in particular 0 to 0.5% by weight, of one or more monomers M7, based on the total weight of the monomers M; the total amount of monomers M1 and M2 is at least 85% by weight, in particular at least 90% by weight, in particular at least 95% by weight, based on the total amount of ethylenically unsaturated monomers M, or, i. cyclopentyl methacrylate as monomer M1, in which at least 10 to 68.95% by weight, in particular 15 to 63.4% by weight, in particular 15 to 57.4% by weight, of the carbon atoms of the cyclopentyl groups in the cyclopentyl methacrylate are of biological origin, based on the total amount of monomers M, in particular the biocarbon content of the cyclopentyl methacrylate is at least 51 mol %, in particular at least 55 mol %; ii. isobutyl acrylate as monomer M2, in which at least 30 to 70% by weight, in particular 35 to 65% by weight, in particular 40 to 60% by weight, of the carbon atoms of the isobutyl groups in the isobutyl acrylate are of biological origin, based on the total amount of monomers M, and in particular the biocarbon content of the isobutyl methacrylate is at least 54 mol %, in particular at least 57 mol %, iii. 1 to 35% by weight, in particular 1.5 to 30% by weight, in particular 2 to 25% by weight, of monomers M3 selected from methyl methacrylate, styrene and combinations thereof, based on the total amount of monomers M; iv. 0.05 to 5 wt. %, in particular 0.1 to 4 wt. %, in particular 0.5 to 3 wt. % of one or more monoethylenically unsaturated monomers M4 selected from acrylic acid, methacrylic acid, itaconic acid and combinations thereof, based on the total amount of monomers M; v. 0 to 9.95 wt. %, in particular 0.05 to 5 wt. %, in particular 0.1 to 4 wt. %, based on the total weight of the monomers M, of one or more nonionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20° C. and 1 bar and having functional groups selected from the group consisting of hydroxyalkyl groups, primary carboxamide groups, urea groups, keto groups, and combinations thereof; and vi. 0 to 1% by weight, in particular 0 to 0.5% by weight, of one or more monomers M7, based on the total weight of the monomers M; the total amount of monomers M1 and M3 is in the range of 5 to 70% by weight, in particular in the range of 10 to 65% by weight, in particular in the range of 15 to 60% by weight, based on the total amount of ethylenically unsaturated monomers M, and the total amount of monomers M1, M2 and M3 is at least 85% by weight, in particular at least 90% by weight, in particular at least 95% by weight, based on the total amount of ethylenically unsaturated monomers M, or, i. cyclopentyl methacrylate as monomer M1, in which at least 10 to 68.95% by weight, in particular 15 to 63.4% by weight, in particular 15 to 57.4% by weight, of the carbon atoms of the cyclopentyl groups in the cyclopentyl methacrylate are of biological origin, based on the total amount of monomers M, in particular the biocarbon content of the cyclopentyl methacrylate is at least 51 mol %, in particular at least 55 mol %; ii. 30 to 70% by weight, in particular 35 to 65% by weight, in particular 40 to 60% by weight, of isobutyl acrylate and at least one C2-C acrylate other than isobutyl acrylate, based on the total amount of monomers M. 10 monomers M2, which are mixtures with alkyl acrylates, such as n-butyl acrylate, isoamyl acrylate, 2-methylbutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate, in which at least the carbon atoms of the isobutyl group in the isobutyl acrylate are of biological origin, and in particular the isobutyl methacrylate has a biocarbon content of at least 54 mol %, in particular at least 57 mol %; iii. 1 to 35% by weight, in particular 1.5 to 30% by weight, in particular 2 to 25% by weight, of monomers M3 selected from methyl methacrylate, styrene and combinations thereof, based on the total amount of monomers M; iv. 0.05 to 5% by weight, in particular 0.1 to 4% by weight, in particular 0.5 to 3% by weight, of one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having an acidic group, based on the total amount of monomers M, v. 0 to 9.95% by weight, in particular 0.05 to 5% by weight, in particular 0.1 to 4% by weight, of one or more non-ionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20° C. and 1 bar, based on the total weight of the monomers M; vi. 0 to 1% by weight, in particular 0 to 0.5% by weight, of one or more monomers M7, based on the total weight of the monomers M; the total amount of monomers M1 and M3 is in the range of 5 to 70% by weight, in particular in the range of 10 to 65% by weight, in particular in the range of 15 to 60% by weight, based on the total amount of ethylenically unsaturated monomers M, and the total amount of monomers M1, M2 and M3 is at least 85% by weight, in particular at least 90% by weight, in particular at least 95% by weight, based on the total amount of ethylenically unsaturated monomers M, or, i. cyclopentyl methacrylate as monomer M1, in which at least 10 to 68.95% by weight, in particular 15 to 63.4% by weight, in particular 15 to 57.4% by weight, of the carbon atoms of the cyclopentyl groups in the cyclopentyl methacrylate are of biological origin, based on the total amount of monomers M, in particular the biocarbon content of the cyclopentyl methacrylate is at least 51 mol %, in particular at least 55 mol %; ii. 30 to 70% by weight, in particular 35 to 65% by weight, in particular 40 to 60% by weight, of n-butyl acrylate or n-butyl acrylate and at least one C2-C acrylate other than n-butyl acrylate, based on the total amount of monomers M. 10 Monomers M2 which are mixtures of alkyl acrylates, for example isoamyl acrylate, 2-methylbutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate, iii. 1 to 35% by weight, in particular 1.5 to 30% by weight, in particular 2 to 25% by weight, of monomers M3 selected from methyl methacrylate, styrene and combinations thereof, based on the total amount of monomers M; iv. 0.05 to 5% by weight, in particular 0.1 to 4% by weight, in particular 0.5 to 3% by weight, of one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having an acidic group, based on the total amount of monomers M, v. 0 to 9.95% by weight, in particular 0.05 to 5% by weight, in particular 0.1 to 4% by weight, of one or more non-ionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20° C. and 1 bar, based on the total weight of the monomers M; vi. 0 to 1% by weight, in particular 0 to 0.5% by weight, of one or more monomers M7, based on the total weight of the monomers M; the total amount of monomers M1 and M3 is in the range of 5 to 70% by weight, in particular in the range of 10 to 65% by weight, in particular in the range of 15 to 60% by weight, based on the total amount of ethylenically unsaturated monomers M, and the total amount of monomers M1, M2 and M3 is at least 85% by weight, in particular at least 90% by weight, in particular at least 95% by weight, based on the total amount of ethylenically unsaturated monomers M.

[0090] In a specific group 4 of embodiments, the types and amounts of the monomers M1, M2, M3, M4 and, if present, M5, M6, M7 or M8 are as defined in specific group 3 of embodiments, except that the monomer M1 is a mixture comprising at least 50% by weight, in particular at least 80% by weight, in particular at least 90% by weight, of cyclopentyl acrylate and cyclopentyl methacrylate instead of cyclopentyl methacrylate, based on the total amount of the monomers M1.

[0091] Preferably, the copolymer particles contained in the polymer latex have a Z-average 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 may be unimodal or nearly unimodal, meaning that the particle size distribution function has a single maximum and no specific shoulder. The particle size distribution of the copolymer particles contained in the polymer latex may be multimodal or nearly multimodal, meaning that the particle size distribution function has at least two distinct maxima or at least one maximum and at least a pronounced shoulder.

[0092] Unless otherwise specified, particle size and size distribution are determined by quasi-elastic light scattering (QELS), also known as dynamic light scattering (DLS). The measurement method is described in the ISO 13321:1996 standard. Determinations can be performed using a high-performance particle size analyzer (HPPS). For this purpose, a sample of the aqueous polymer latex is diluted and the 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 is 0.01% by weight. However, higher or lower concentrations may be used to achieve an optimal signal-to-noise ratio. Dilution can be achieved by adding the polymer latex to water or an aqueous solution of a surfactant to avoid aggregation. Typically, dilution is performed using a 0.1% by weight aqueous solution of a nonionic emulsifier, such as an ethoxylated C16 / C18 alkanol (degree of ethoxylation 18), as the diluent. Measurement configuration: Malvern HPPS, automated, continuous-flow cuvettes and Gilson autosampler. Parameters: Measurement temperature 20.0°C; Measurement time 120 seconds (6 cycles every 20 seconds); Scattering angle 173°; Laser wavelength 633 nm (HeNe); Refractive index of medium 1.332 (aqueous); Viscosity 0.9546 mPa·s. The measurement yields the average value of the second-order cumulant analysis (fitting average), i.e., the Z-average. The "fitting average" is the average intensity-weighted hydrodynamic particle size in nm.

[0093] Hydrodynamic particle size can also be determined by hydrodynamic chromatography fractionation (HDC), for example, as described in H. Wiese, "Characterization of Aqueous Polymer Dispersions" in Polymer Dispersions and Their Industrial Applications (Wiley-VCH, 2002), pp. 41-73. For further details, see the examples and discussion below.

[0094] In a particular group of embodiments, the copolymer particles contained in the polymer latex have a Z-average particle size, as determined by QELS, in the range of 30 to 200 nm, in particular in the range of 40 to 150 nm. In this particular group of embodiments, the particle size distribution of the copolymer particles contained in the polymer latex is in particular unimodal or nearly unimodal, meaning that the particle size distribution function has a single maximum.

[0095] The copolymers contained in the polymer particles may form a single phase or may form different phases if the polymer particles contain different copolymers that 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 not exceeding 40°C, in particular at most 25°C, preferably in the range of -25 to +40°C, in particular in the range of -20 to +25°C.

[0096] The glass transition temperatures referred to herein are actual glass transition temperatures, which can be determined experimentally by differential scanning calorimetry (DSC) methods, with samples prepared according to ISO 11357-2:2013, preferably according to ISO 16805:2003.

[0097] The actual glass transition temperature depends on the monomer composition that forms the polymer, and the theoretical glass transition temperature can be calculated from the monomer composition used in the emulsion polymerization. The theoretical glass transition temperature is usually calculated from the monomer composition by the Fox equation: 1 / Tg t =x a / Tg a +x b / Tg b +....x n / Tg n ,

[0098] In this formula, x a , x b ,....x n are the mass fractions of monomers a, b, ....n, and Tg a , Tg b ,....Tg nis the actual glass transition temperature in Kelvin of a homopolymer synthesized from only one of the monomers 1, 2, ....n at a time. The Fox formula is explained by T.G. Fox in Bull. Am. Phys. Soc. 1956, 1, page 123, and also in Ullmann's Encyclopadie der technischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], vol. 19, p. 18, 4th ed., Verlag Chemie, Weinheim, 1980. Actual Tg values ​​for homopolymers of most monomers are known and are listed, for example, in Ullmann's Encyclopadie der technischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], 5th ed., vol. A21, p. 169, Verlag Chemie, Weinheim, 1992. Further sources of information on the glass transition temperatures of homopolymers are, for example, J. Brandrup, E.H. Immergut, Polymer Handbook, 1st Ed., J. Wiley, New York 1966, 2nd Ed. J. Wiley, New York 1975, 3rd Ed. J. Wiley, New York 1989 and 4th Ed. J. Wiley, New York 2004.

[0099] Typically, the theoretical glass temperature Tg calculated according to Fox as described herein t and the experimentally determined glass transition temperatures described herein are similar or the same and do not deviate from each other by more than 5 K, and in particular do not deviate by more than 2 K. Therefore, both the actual and theoretical glass transition temperatures of polymer phases (1) and (2) are determined by the appropriate monomers Ma, Mb...Mn and their mass fractions x in the monomer composition to reach the desired glass transition temperatures Tg(1) and Tg(2), respectively. a , x b ,....x nIt is common knowledge for a person skilled in the art to select the appropriate amounts of monomers Ma, Mb...Mn to obtain a copolymer and / or copolymer phase with a desired glass transition temperature.

[0100] Preferably, the aqueous polymer latex of the present invention has a pH of at least 3, for example, in the range of pH 3 to pH 11.5.

[0101] The aqueous polymer dispersions of the present invention generally have a solids content in the range of 30 to 75% by weight, in particular in the range of 40 to 65% by weight, preferably in the range of 45 to 60% by weight. The solids content represents the proportion of non-volatile matter. The solids content of a dispersion is determined by balance with infrared moisture analysis. For this determination, a certain amount of polymer dispersion is introduced into the instrument, heated to 140°C, and then maintained at that temperature. As soon as the average weight loss falls below 1 mg within 140 seconds, the measurement procedure is terminated. The ratio of the weight after drying to the original mass introduced gives the solids content of the polymer dispersion. The total solids content of a formulation is determined arithmetically from the amount of added substances and their solids content and concentration.

[0102] If the polymer in the polymer latex has a functional group complementary to the functional group of the crosslinking agent, the polymer dispersion may contain a crosslinking agent to achieve post-crosslinking of the polymer latex particles. In this context, the term "complementary" should be understood to mean that the functional groups of the latex and the functional groups of the crosslinking agent are susceptible to chemical reactions that form chemical bonds between the atoms of the respective functional groups. Typically, the crosslinking agent has at least two functional groups complementary to the functional groups of the polymer in the polymer latex. Examples of suitable crosslinking agents are described below.

[0103] In addition to the polymer and optional crosslinker, the aqueous polymer dispersion of the present invention may contain additional components conventionally present in aqueous polymer dispersions. These additional components include, for example, surface-active compounds, such as emulsifiers and protective colloids, especially those used in the preparation of polymer latexes, additional defoamers, etc. Additional components may include acids, bases, buffers, decomposition products from the polymerization reaction, deodorizing compounds, and chain transfer agents. Furthermore, the polymer latex may contain biodegradants to prevent microbial spoilage. The amount of each individual component typically does not exceed 1.5% by weight based on the total weight of the polymer dispersion. The total amount of these listed components typically does not exceed 5% by weight based on the total weight of the polymer latex.

[0104] Preferably, the amount of volatile organics, i.e. the content of organic compounds having a boiling point of up to 250°C under standard conditions (101,325 kPa) as determined by gas chromatography according to ISO 17895:2005, is less than 0.5% by weight, in particular less than 0.2% by weight, based on the total weight of the polymer latex.

[0105] In addition to the polymer, the aqueous polymer latex also contains an aqueous phase, in which the polymer particles of the polymer latex are dispersed.The aqueous phase, also called serum, essentially consists of water and any water-soluble additional components.The total concentration of any additional components is typically not more than 10% by weight, particularly not more than 8% by weight, based on the total weight of the aqueous phase.

[0106] The aqueous polymer latex of the present invention can be prepared by any method for preparing an aqueous dispersion of a polymer made from polymerized monomer M. In particular, the aqueous polymer latex of the present invention is prepared by aqueous emulsion polymerization, particularly 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 radicals formed by the decay of a polymerization initiator, thereby forming free radicals in the polymerization mixture. Therefore, it is also called "radical-initiated emulsion polymerization." The procedure for the radical-initiated emulsion polymerization of monomers in aqueous medium has been extensively described and is therefore well known to those skilled in the art [see, in this regard, Emulsion Polymerization in Encyclopedia of Polymer Science and Engineering, vol. 8, pages 659 ff. (1987); D.C. Blackley, in High Polymer Latices, vol. 1, pages 35 ff. (1966); H. Warson, The Applications of Synthetic Resin Emulsions, chapter 5, pages 246 ff. (1972); D. Diederich, Chemie in unserer Zeit 24, pages 135 to 142 (1990); Emulsion Polymerisation, Interscience Publishers, New York (1965); DE-A-40 03 422; and Dispersionen synthetischer Hochpolymerer, F. Holscher, Springer-Verlag, Berlin (1969)]. Typical procedures for the aqueous emulsion polymerization of ethylenically unsaturated monomers are also described in the patent literature discussed in the introductory part of this patent application.

[0107] Radical-initiated aqueous emulsion polymerization is typically carried out by emulsifying ethylenically unsaturated monomers in an aqueous medium, forming an aqueous phase, typically with the use of surface-active compounds, such as emulsifiers and / or protective colloids, and polymerizing the system using at least one initiator, which decomposes with the formation of radicals, thereby initiating the chain-growth addition polymerization of the ethylenically unsaturated monomers M. The preparation of aqueous polymer dispersions according to the present invention may differ from this general procedure only in the specific use of the monomers M1 through M8 described above. For purposes of this specification, the process will be understood to encompass seeded, staged, one-shot, and gradient regimes, all of which are familiar to those skilled in the art.

[0108] Free-radical initiated aqueous emulsion polymerization is initiated by a free-radical polymerization initiator (free-radical initiator). These can, in principle, be peroxides or azo compounds. Of course, redox initiator systems are also useful. The peroxides used can, in principle, be inorganic peroxides, such as hydrogen peroxide or peroxodisulfates, for example, mono- or di-alkali metal or ammonium salts of peroxodisulfate, such as mono- and disodium, potassium, or ammonium salts, or organic peroxides, such as alkyl hydroperoxides, for example, tert-butyl hydroperoxide, p-menthyl hydroperoxide, or cumyl hydroperoxide, and dialkyl or diaryl peroxides, for example, di-tert-butyl or di-cumyl peroxide. The azo compounds used are essentially 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile) and 2,2'-azobis(amidinopropyl) dihydrochloride (AIBA corresponds to V-50 from Wako Chemicals). Suitable oxidizing agents for the redox initiator system are essentially the peroxides mentioned above. Corresponding reducing agents which may be used are sulfur compounds in a low oxidation state, such as alkali metal sulfites, for example potassium sulfite and / or sodium sulfite, alkali metal hydrogen sulfites, for example potassium hydrogen sulfite and / or sodium hydrogen sulfite, alkali metal metabisulfites, for example potassium metabisulfite and / or sodium metabisulfite, formaldehyde sulfoxylates, for example potassium and / or sodium formaldehyde sulfoxylate, alkali metal salts, in particular potassium and / or sodium salts of aliphatic sulfinic acids and alkali metal hydrogen sulfides, for example potassium hydrogen sulfide and / or sodium hydrogen sulfide, salts of polyvalent metals, for example iron(II) sulfate, ammonium iron(II) sulfate, iron(II) phosphate, enediols, for example dihydroxymaleic acid, benzoin and / or ascorbic acid, and reduced saccharides, for example sorbose, glucose, fructose and / or dihydroxyacetone.

[0109] Preferred free radical initiators are inorganic peroxides, especially peroxodisulfates.

[0110] Generally, the amount of free radical initiator used based on the total amount of monomers M is from 0.05 to 2 pphm, preferably from 0.1 to 1 pphm, based on the total amount of monomers M.

[0111] The amount of free radical initiator required for the emulsion polymerization of monomer M can be initially charged completely to the polymerization vessel. However, it is also possible to charge none or only a portion of the free radical initiator, for example, not more than 30% by weight, particularly not more than 20% by weight, based on the total amount of free radical initiator, and then add any remaining amount of free radical initiator 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 to the free radical polymerization reaction under polymerization conditions. The feeding of the monomers during the free radical emulsion polymerization of monomer M can be carried out batchwise in one or more portions, or continuously, at a constant or variable flow rate, depending on the consumption.

[0112] Generally, the term "polymerization conditions" is understood to mean the temperature and pressure at which the free radical initiated aqueous emulsion polymerization proceeds at a sufficient polymerization rate. They depend, inter alia, on the free radical initiator used. Advantageously, the type and amount of free radical initiator, the polymerization temperature and the polymerization pressure are selected so that a sufficient amount of initiating radicals is always present to initiate or sustain the polymerization reaction.

[0113] Preferably, the radical emulsion polymerization of the monomers M is carried out by the so-called feeding process (also called the monomer feeding method), which means that at least 80%, particularly at least 90%, or the total amount of the monomers M to be polymerized is metered into the polymerization reaction under polymerization conditions during a metering period P. The addition may be carried out partially, preferably continuously, at a constant or variable feed rate. The duration of period P may depend on the production equipment and may vary, for example, from 20 minutes to 12 hours. In many cases, the duration of period P ranges from 0.5 hours to 8 hours, particularly from 1 hour to 6 hours. In a multistage emulsion polymerization process, the total duration of all steps is typically within the above range. The duration of the individual steps is typically shorter. Preferably, at least 70%, particularly at least 80%, and particularly at least 90%, or the total amount of the polymerization initiator is introduced into the emulsion polymerization in parallel with the addition of the monomers.

[0114] Aqueous radical emulsion polymerization is usually carried out in the presence of one or more suitable surfactants. These surfactants typically contain emulsifiers and provide the micelles in which polymerization occurs, stabilizing the monomer droplets during aqueous emulsion polymerization and also aiding in the growth of polymer particles. The surfactants used in emulsion polymerization are usually not separated from the polymer dispersion but remain in the aqueous polymer dispersion obtained by emulsion polymerization of monomer M.

[0115] The surfactant can be selected from emulsifiers and protective colloids. Protective colloids are understood to mean polymeric compounds with a molecular weight of more than 2000 Daltons, in contrast to emulsifiers, while emulsifiers typically have a lower molecular weight. The surfactant can be anionic or nonionic, or a mixture of nonionic and anionic surfactants.

[0116] Anionic surfactants usually have at least one anionic group, typically selected from phosphate group, phosphonate group, sulfate group and sulfonate group.Anionic surfactants having at least one anionic group are typically used in the form of their alkali metal salt, particularly their sodium salt, or their ammonium salt.

[0117] Preferred anionic surfactants are anionic emulsifiers, especially those having at least one sulfate or sulfonate group.Similarly, anionic emulsifiers having at least one phosphate or phosphonate group can be used as the sole anionic emulsifier or in combination with one or more anionic emulsifiers having at least one sulfate or sulfonate group.

[0118] Examples of anionic emulsifiers having at least one sulfate or sulfonate group are, for example: -Alkyl sulfates, especially C8-C 22 salts of alkyl sulfates, in particular the alkali metal and ammonium salts; - Sulfuric acid monoesters of ethoxylated alkanols, preferably with an ethoxylation level (EO level) ranging from 2 to 40, in particular ethoxylated C8-C 22 salts of sulfuric acid monoesters of alkanols, in particular the alkali metal and ammonium salts, -Alkyl sulfonic acids, especially C8-C 22 the salts of alkylsulfonic acids, in particular the alkali metal and ammonium salts, -Dialkyl esters, especially diC4-C of sulfosuccinic acid 18 the salts of alkyl esters, in particular the alkali metal and ammonium salts, -Alkylbenzenesulfonic acids, especially C4-C 22 salts of alkylbenzenesulfonic acids, in particular the alkali metal and ammonium salts, and Mono- or disulfonated alkyl-substituted diphenyl ethers, e.g., C4-C on one or both aromatic rings 24- Salts of alkyl-containing bis(phenylsulfonic acid) ethers, especially alkali metal and ammonium salts The latter is common knowledge, for example from U.S. Pat. No. 4,269,749, and is commercially available, for example, as Dowfax® 2A1 (Dow Chemical Company), - surfactants having a polymerizable ethylenically unsaturated double bond as described herein, such as those represented by formulas (I) to (IV) (wherein X and Y are each SO3 - or O-SO3 - is a compound of

[0119] Examples of anionic emulsifiers having phosphate or phosphonate groups, including but not limited to salts of the following, are selected from the group: -mono- and dialkyl phosphates, especially C8-C 22 salts of alkyl phosphates, in particular the alkali metal and ammonium salts, - salts, in particular alkali metal and ammonium salts, of phosphoric acid monoesters of C2-C3-alkoxylated alkanols, preferably with an alkoxylation level in the range from 2 to 40, in particular in the range from 3 to 30; for example ethoxylated C8-C6 alkoxylated alkanols, preferably with an ethoxylation level (EO level) in the range from 2 to 40. 22 - propoxylated C8-C phosphoric acid monoesters of alkanols, preferably with a propoxylation level (PO level) ranging from 2 to 40; 22 - Phosphoric acid monoesters of alkanols and ethoxylated co-propoxylated C8-C, preferably with an ethoxylation level (EO level) ranging from 1 to 20 and a propoxylation level from 1 to 20. 22 -phosphoric acid monoesters of alkanols, -Alkylphosphonic acids, especially C8-C 22 salts of alkylphosphonic acids, in particular the alkali metal and ammonium salts, and -Alkylbenzenephosphonic acids, especially C4-C 22 salts of alkylbenzenephosphonic acids, in particular the alkali metal and ammonium salts, - surfactants having a polymerizable ethylenically unsaturated double bond as described herein, for example, compounds of formula (I) to (IV), where X and Y are each HPO3 - , PO3 2 , O-HPO3 - or O-PO3 2 (It is).

[0120] Anionic emulsifiers may also include emulsifiers having a polymerizable double bond, such as emulsifiers of formulae (I) to (IV) and salts thereof, particularly alkali metal or ammonium salts thereof. [ka]

[0121] In formula (I), R 1 is H, C1-C 20 -Alkyl, C5-C 10 -Cycloalkyl, C1-C 20 -phenyl optionally substituted with alkyl, and R 2 and R 2’ are both H or together are O, and R 3 and R 4 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- is. [ka]

[0122] In formula (II), R is H, C1-C 20 -Alkyl, C5-C 10 -Cycloalkyl, C1-C 20 -phenyl optionally substituted with alkyl, k is 0 or 1, and X is SO3 - , O-SO3 - , O-HPO3 - or O-PO32- is. [ka]

[0123] In formula (III), R 1 is H, C1-C 20 -Alkyl, O-C1-C 20 -Alkyl, C5-C 10 -Cycloalkyl, O-C5-C 10 -Cycloalkyl, C1-C 20 -O-phenyl optionally substituted with alkyl, n is an integer of 1 to 100, and Y is SO3 - , HPO3 - or PO3 2- is. [ka]

[0124] In formula (IV), R 1 is H, C1-C 20 -alkyl or 1-phenylethyl, and R 2 is H, C1-C 20 -alkyl or 1-phenylethyl, A is C2-C4-alkanediyl, for example 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- is.

[0125] Particular embodiments of copolymerizable emulsifiers of formula (I) are referred to as sulfate or phosphate esters of polyethylene glycol monoacrylate. Particular embodiments of copolymerizable emulsifiers of formula (I) may also be referred to as phosphonate esters or allyl ether sulfates of polyethylene glycol monoacrylate. Commercially available copolymerizable emulsifiers of formula (I) are Maxemul® emulsifier, Sipomer® PAM emulsifier, Latemul® PD, and ADEKA Reasoap® PP-70.

[0126] A particular embodiment of the copolymerizable emulsifier of formula (II) is also referred to as alkylaryl sulfosuccinate. A commercially available copolymerizable emulsifier of formula (II) is Trem® LF40.

[0127] Particular embodiments of copolymerizable emulsifiers of formula (III) are also referred to as branched unsaturated. Commercially available copolymerizable emulsifiers of formula (III) are Adeka® Reasoap emulsifier and Hitenol® KH.

[0128] Particular embodiments of copolymerizable emulsifiers of formula (IV) are also referred to as polyoxyethylene alkylphenyl ether sulfates and polyoxyethylene mono- or distyrylphenyl ether sulfates. Commercially available copolymerizable emulsifiers of formula (IV) are Hitenol® BC and Hitenol® AR emulsifiers.

[0129] Further suitable anionic surfactants can be found in Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], volume XIV / 1, Makromolekulare Stoffe [Macromolecular Substances], Georg-Thieme-Verlag, Stuttgart, 1961, pp. 192-208.

[0130] 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 can 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 can also be used. In such a mixture, the amount of at least one anionic emulsifier having at least one sulfate or sulfonate group is preferably at least 50 wt.% based on the total weight of the anionic surfactant used in the method of the present invention. In particular, the amount of the anionic emulsifier having at least one phosphate or phosphonate group does not exceed 20 wt.% based on the total weight of the anionic surfactant used in the method of the present invention.

[0131] Preferred anionic surfactants are anionic emulsifiers selected from the following group (including mixtures thereof): -Alkyl sulfates, especially C8-C 22 salts of alkyl sulfates, in particular the alkali metal and ammonium salts; - sulfuric acid monoesters of ethoxylated alkanols, preferably with an ethoxylation level (EO level) ranging from 2 to 40, in particular ethoxylated C8-C 22 salts of sulfuric acid monoesters of alkanols, in particular the alkali metal salts; - Sulfuric acid monoesters of ethoxylated alkylphenols, especially ethoxylated C4-C 18 - sulfuric acid monoesters of alkylphenols (EO level, preferably 3 to 40), -Alkylbenzenesulfonic acids, especially C4-C 22 alkylbenzene sulfonic acids, and Mono- or disulfonated alkyl-substituted diphenyl ethers, e.g., C4-C on one or both aromatic rings 24 -Bis(phenylsulfonic acid) ethers having alkyl groups. - a polymerizable emulsifier of formula (III):

[0132] Particularly preferred are anionic emulsifiers selected from the following group (including mixtures thereof): -Alkyl sulfates, especially C8-C 22 salts of alkyl sulfates, in particular the alkali metal and ammonium salts; - sulfuric acid monoesters of ethoxylated alkanols, preferably with an ethoxylation level (EO level) ranging from 2 to 40, in particular ethoxylated C8-C 22 salts of sulfuric acid monoesters of alkanols, in particular the alkali metal salts; Mono- or disulfonated alkyl-substituted diphenyl ethers, e.g., C4-C on one or both aromatic rings 24 -Bis(phenylsulfonic acid) ethers having alkyl groups. - Formula (III) (wherein Y is SO3 - ) a polymerizable emulsifier.

[0133] Similar to the aforementioned anionic surfactants, the surfactant may also comprise one or more nonionic surface-active substances, in particular selected from nonionic emulsifiers. Suitable nonionic emulsifiers are, for example, araliphatic or aliphatic nonionic emulsifiers, such as ethoxylated mono-, di- and trialkylphenols (EO level: 3 to 50, alkyl radical: C4-C6). 10 ), ethoxylates of long-chain alcohols (EO level: 3 to 100, alkyl radical: C8-C 36 ), and polyethylene oxide / polypropylene oxide homopolymers and copolymers. These may contain copolymerized alkylene oxide units in random distribution or in the form of blocks. Highly suitable examples are EO / PO block copolymers. Ethoxylates of long-chain alkanols, especially those with alkyl radicals C8-C 30 Preferred are those having an average ethoxylation level of 5 to 100, and among these, linear C 12 -C 20Those having alkyl radicals and average ethoxylation levels of 10 to 50 are particularly preferred, as are ethoxylated monoalkylphenols.

[0134] The surfactant used in the method of the present invention typically contains no more than 30% by weight, particularly no more than 20% by weight, of nonionic surfactants, based on the total amount of surfactants used in the method of the present invention, and is particularly free of 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 amount of anionic surfactants to the total amount of nonionic surfactants is in the range of 99:1 to 70:30, particularly in the range of 98:2 to 75:25, and particularly in the range of 95:5 to 80:20.

[0135] Preferably, the surfactant is used in an amount such that the amount of surfactant is in the range of 0.2 to 5% by weight, in particular in the range of 0.3 to 4.5% by weight, based on the monomers M to be polymerized. In multi-stage emulsion polymerizations, the surfactant is used in an amount such that the amount of surfactant is usually in the range of 0.2 to 5% by weight, in particular in the range of 0.3 to 4.5% by weight, based on the total amount of monomers polymerized in each stage.

[0136] Preferably, the majority, i.e., at least 80% of the surfactant used, is added to the emulsion polymerization in parallel with the addition of the monomers, particularly the monomers are added to the polymerization reaction as an aqueous emulsion containing at least 80% of the surfactant used in the emulsion polymerization.

[0137] It has been found to be advantageous to carry out the free radical emulsion polymerization of monomer M in the presence of a seed latex. The seed latex is a polymer latex that is present in the aqueous polymerization medium before the polymerization of monomer M is initiated. The seed latex can serve to better control the particle size or final polymer latex obtained in the free radical emulsion polymerization of the present invention.

[0138] Basically, any polymer latex can serve as a seed latex. For the purposes of the present invention, seed latexes in which the particle size of the polymer particles is relatively small are preferred. In particular, the Z-average particle size of the polymer particles of the seed latex, determined by dynamic light scattering (DLS) (see below) at 20°C, is preferably in the range of 10 to 80 nm, in particular 10 to 50 nm. Preferably, the polymer particles of the seed latex contain at least 95% by weight of C2-C acrylic acid, based on the total weight of the monomers forming the seed latex. 10 The seed latex is made from ethylenically unsaturated monomers, including one or more monomers selected from the group consisting of alkyl esters, in particular ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, C1-C4-alkyl methacrylates, such as methyl methacrylate, monoethylenically unsaturated nitriles, such as acrylonitrile, and the vinyl aromatic monomers defined above, such as styrene, and mixtures thereof. In particular, the polymer particles of the seed latex are made from at least 95% by weight of ethylenically unsaturated monomers, based on the total weight of the monomers forming the seed latex, including one or more monomers selected from the group consisting of C1-C4-alkyl methacrylates, such as methyl methacrylate, monoethylenically unsaturated nitriles, such as acrylonitrile, and the vinyl aromatic monomers defined above, such as styrene, and mixtures thereof.

[0139] For this reason, the seed latex is usually charged to the polymerization vessel before starting the polymerization of the monomer M. In particular, the seed latex is charged to the polymerization vessel, and then the polymerization conditions are established, for example, by heating the mixture to the polymerization temperature. It may be advantageous to charge at least a portion of the free radical initiator to the polymerization vessel before starting the addition of the monomer M. However, it is also possible to add the monomer M and the free radical polymerization initiator to the polymerization vessel in parallel.

[0140] The amount of seed latex, calculated as solids, may often be in the range of 0.01 to 10% by weight, preferably in the range of 0.05 to 5% by weight, in particular in the range of 0.05 to 3% by weight, based on the total weight of the monomers in the monomer composition M to be polymerized.

[0141] The free radical aqueous emulsion polymerization of the present invention can be carried out at temperatures ranging from 0 to 170°C. The temperatures used are generally in the range of 50 to 120°C, often 60 to 120°C, and often 70 to 110°C. The free radical aqueous emulsion polymerization of the present invention can be carried out at pressures below 1 atm (atmospheric pressure) and above 1 atm, so that the polymerization temperature can exceed 100°C, even up to 170°C. The polymerization of the monomers is usually carried out at atmospheric pressure, but can also be carried out under elevated pressure. In this case, the pressure can be 1.2, 1.5, 2, 5, 10, 15 bar (absolute) or even higher. When the emulsion polymerization is carried out under reduced pressure, a pressure of 950 mbar, often 900 mbar, often 850 mbar (absolute) is established. Advantageously, the free radical aqueous emulsion polymerization of the present invention is carried out at ambient pressure (about 1 atm) with the exclusion of oxygen, for example, under an inert gas atmosphere, such as nitrogen or argon.

[0142] The process for producing the polymer latex of the present invention may be a single-stage polymerization or a multi-stage emulsion polymerization, in which the total composition of the monomers M fed to the polymerization reaction under polymerization conditions remains the same or nearly the same, whereas in a multi-stage emulsion polymerization, the total composition of the monomers M fed to the polymerization reaction under polymerization conditions is changed at least once, particularly so that the theoretical glass transition temperature of the resulting polymer formed in one stage differs from the theoretical glass transition temperature of the resulting polymer formed in another stage by at least 10°C, particularly at least 20°C or at least 40°C.

[0143] In a particular group of embodiments, the process of the present invention is carried out as a two-stage emulsion polymerization, i.e., the composition of the monomers fed to the polymerization reaction under polymerization conditions is corrected once, or as a three-stage or four-stage emulsion polymerization, i.e., the composition of the monomers fed to the polymerization reaction under polymerization conditions is corrected twice or three times.

[0144] The polymerization of the monomers M can optionally be carried out in the presence of a chain transfer agent, which is understood to mean a compound that transfers free radicals, reduces the molecular weight of the growing chains and / or controls the chain growth in the polymerization. Examples of chain transfer agents are aliphatic and / or araliphatic halogen compounds, such as n-butyl chloride, n-butyl bromide, n-butyl iodide, methylene chloride, ethylene dichloride, chloroform, bromoform, bromotrichloromethane, dibromodichloromethane, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide; organic thio compounds, such as primary, secondary or tertiary aliphatic thiols, 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, thiol, 2-methyl-3-pentanethiol, 3-methyl-3-pentanethiol, 2-ethylbutanethiol, 2-ethyl-2-butanethiol, n-heptanethiol and its isomeric compounds, n-octanethiol and its isomeric compounds, n-nonanethiol and its isomeric compounds, n-decanethiol and its isomeric compounds, n-undecanethiol and its isomeric compounds, n-dodecanethiol and its isomeric compounds, n-tridecanethiol and its isomeric compounds, substituted thiols such as 2-hydroxyethanethiol, aromatic thiols such as benzenethiol, ortho-, meta- or para-methylbenzenethiol, alkyl esters of mercaptoacetic acid (thioglycolic acid), such as 2-ethylhexyl thioglycolate, alkyl esters of mercaptopropionic acid, such as octylmercaptopropionate, and furthermore, Polymer Handbook, 3rd edition, 1989, J. Brandrup and EHFurther sulfur compounds are listed in Immergut, John Wiley & Sons, section II, 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 easily abstractable hydrogen atoms, such as toluene.

[0145] Alternatively, it is possible to use a mixture of the aforementioned chain transfer agents that do not destroy each other. Optionally, the total amount of chain transfer agents used in the process of the present invention generally does not exceed 2% by weight, in particular 1% by weight, based on the total amount of monomers M. However, during a certain period of the polymerization reaction, the amount of chain transfer agent added to the polymerization reaction may exceed the value of 2% by weight, and may be as high as 8% by weight, in particular up to 4% by weight, based on the total amount of monomers M added to the polymerization reaction during said period.

[0146] It is often advantageous to subject the aqueous polymer dispersion obtained upon completion of the polymerization of the monomers M to a post-treatment to reduce the residual monomer content. This post-treatment can be carried out chemically, for example by completing the polymerization reaction using a more efficient free-radical initiator system (known as post-polymerization), and / or physically, for example by stripping the aqueous polymer dispersion with steam or an inert gas. Corresponding chemical and physical methods are well known to those skilled in the art, see, for example, EP-A-771328, DE-A-19624299, DE-A-19621027, DE-A-19741184, DE-A-19741187, DE-A-19805122, DE-A-19828183, DE-A-19839199, DE-A-19840586 and DE-A-19847115. The combination of chemical and physical aftertreatment has the advantage that not only unconverted ethylenically unsaturated monomers but also other destructive volatile organic components (VOCs) are removed from the aqueous polymer dispersion.

[0147] Because the polymer contained in the aqueous polymer dispersion may contain acidic groups from the monomer M4 and, optionally, the polymerization initiator, the aqueous polymer dispersion obtained by the process of the present invention is often neutralized before being formulated into a coating composition. Neutralization of the acidic groups of the polymer is achieved after and / or during polymerization using a neutralizing agent known to those skilled in the art. For example, the neutralizing agent may be added as a co-feed with the monomer to be polymerized or as a separate feed. Suitable neutralizing agents include organic amines, alkali hydroxides, and ammonium hydroxide. In particular, neutralization is achieved using ammonia or alkali hydroxides, such as sodium hydroxide or potassium hydroxide.

[0148] Additionally, it may be advantageous to formulate the polymer latexes of the present invention with a post-curing agent. Ideally, such a post-curing agent, also called a post-crosslinker, will form coordinate or covalent bonds with reactive sites on the surface of the polymer particles, thereby effecting a crosslinking reaction during and / or after film formation.

[0149] Suitable crosslinking agents for providing post-crosslinking include, for example, compounds having at least two functional groups selected from oxazoline, amino, aldehyde, aminoxy, carbodiimide, aziridinyl, epoxy, and hydrazide groups, and derivatives or compounds having acetoacetyl groups. These crosslinking agents react with reactive sites of the polymers of the polymer dispersion that have complementary functional groups in the polymer that can form covalent bonds with the crosslinking agent. Suitable systems are known to those skilled in the art.

[0150] Since the polymer contained in the polymer dispersion of the present invention has carboxyl groups, post-crosslinking can be achieved by blending the polymer dispersion with one or more polycarbodiimides, as described in U.S. Patent No. 4,977,219, U.S. Patent No. 5,047,588, U.S. Patent No. 5,117,059, EP Patent No. 0,277,361, EP Patent No. 0,507,407, EP Patent No. 0,628,582, U.S. Patent No. 5,352,400, U.S. Patent Application Publication No. 2011 / 0151,128, and U.S. Patent Application Publication No. 2011 / 0217,471. Crosslinking is assumed to be based on the reaction of the carboxyl groups of the polymer with the polycarbodiimide. This reaction typically results in covalent crosslinks based primarily on N-acylurea bonds (JW Taylor and DRBassett, in EJ Glass (Ed.), Technology for Waterborne Coatings, ACS Symposium Series 663, Am. Chem. Soc., Washington, DC, 1997, chapter 8, pages 137 to 163).

[0151] Similarly, since the polymer particles contained in the polymer dispersion of the present invention have carboxyl groups derived from monomer M4, suitable post-curing agents may also be water-soluble or water-dispersible polymers having oxazoline groups, such as those described in U.S. Pat. No. 5,300,602 and WO 2015 / 197662.

[0152] Post-crosslinking can also be achieved analogously to EP 1227116, which describes an aqueous two-component coating composition containing a binder polymer with carboxylic acid and hydroxyl functional groups and a multifunctional crosslinker with functional groups selected from isocyanate, carbodiimide, aziridinyl and epoxy groups.

[0153] When the polymer in the polymer dispersion has a keto group, for example, by using a monomer M5c, such as diacetone acrylamide (DAAM), the aqueous polymer dispersion can be post-crosslinked by blending it with one or more dihydrazides, particularly aliphatic dicarboxylic acids, such as adipic acid dihydrazide (ADDH) as described in U.S. Patent No. 4,931,494, U.S. Patent Application Publication No. 2006 / 247367, and U.S. Patent Application Publication No. 2004 / 143058. These components essentially react during and after film formation, but some pre-reaction may occur.

[0154] Other suitable agents for achieving post-cure include: - epoxy silanes to crosslink carboxy groups in the polymer, dialdehydes, such as glyoxal for crosslinking urea or acetoacetoxy groups, such as those derived from the monomers M5b and M5c defined herein, in particular ureido(meth)acrylate or acetoacetoxyethyl(meth)acrylate, respectively; - di- and / or polyamines for crosslinking keto or epoxy groups, for example those derived from monomers M5c or M6b as defined herein, and UV initiators, for example benzophenone, including 4-methoxybenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, acetophenones, such as 2-hydroxy-2,2-dimethylacetophenone, 2-phenyl-2,2-dimethylacetophenone, cycloalkylphenyl ketones, for example 1-benzoylcyclohexan-1-ol (=1-hydroxycyclohexylphenyl ketone) and benzoin, and mixtures thereof, in particular 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. Examples include:

[0155] Suitable systems are described, for example, in EP 355028, EP 441221, EP 0789724, US Pat. No. 5,516,453 and US Pat. No. 5,498,659 and / or are commercially available, for example, in the case of UV initiators from Omnirad and IGM Resins (e.g., Esacure TZM, Esacure TZT, Omnirad 4MBZ).

[0156] The present invention also provides a) a binder polymer in the form of an aqueous polymer latex as defined herein; b) at least one further component conventionally used in water-based coating compositions that is not a binder; and The present invention relates to a water-based coating composition comprising:

[0157] The water-based coating compositions of the present invention may be formulated as clearcoats or paints, in which case the water-based coating composition contains, in addition to the polymer latex, at least one inorganic pigment that imparts a white shade or color to the resulting coating when the water-based coating composition is used to coat a substrate.

[0158] Pigments for the purposes of the present invention are substantially insoluble, finely dispersed, organic or preferably inorganic colorants according to the definition of German Standard DIN 55944:2003-11. Examples of pigments are in particular inorganic pigments, for example white pigments such as titanium dioxide (CI Pigment White 6), but also colored pigments, for example black pigments, such as iron oxide black (CI Pigment Black 11), iron manganese black, spinel black (CI Pigment Black 27), carbon black (CI Pigment Black 7), colored pigments, for example, chromium oxide, chromium oxide hydrate 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 lead (CI Pigment Red 101); cadmium sulfoselenide (CI Pigment Red 108); lead molybdate (CI Pigment Red 104); ultramarine lead, - Iron oxide brown, mixed brown, spinel and corundum phases (CI Pigment Brown 24, 29 and 31), chrome orange, -Iron oxide yellow (CI Pigment Yellow 42); Nickel titanium yellow (CI Pigment Yellow 53; CI Pigment Yellow 157 and 164); Chrome titanium yellow; Cadmium sulfide and cadmium zinc sulfide (CI Pigment Yellow 37 and 35); Chrome yellow (CI Pigment Yellow 34), Zinc yellow, Alkaline earth metal chromates; Napple yellow; Bismuth vanadate (CI Pigment Yellow 184); interference pigments, for example metallic effect pigments based on coated metal platelets, pearlescent pigments based on mica platelets coated with metal oxides, and liquid crystal pigments is.

[0159] The water-based coating composition may also contain one or more fillers. Examples of suitable fillers include aluminosilicates such as feldspar, silicates such as kaolin, talc, mica, and magnesite, alkaline earth metal carbonates such as calcium carbonate in the form of calcite or chalk, magnesium carbonate, dolomite, alkaline earth metal sulfates such as calcium sulfate, silicon dioxide, and the like. Finely divided fillers are naturally preferred in the coating composition of the present invention. Fillers may be used in the form of individual components. However, in practice, filler mixtures such as calcium carbonate / kaolin, calcium carbonate / talc, and the like have been found to be particularly useful. Gloss paints generally contain only small amounts of very finely divided fillers, or none at all. Fillers also contain matting agents, which significantly impair the desired gloss. Matting agents are generally transparent and may be organic or inorganic. Examples of matting agents are inorganic silicates, such as the Syloid® brand from W.R. Grace & Company and the Acematt® brand from Evonik GmbH. Organic matting agents are available, for example, from BYK-Chemie GmbH under the Ceraflour® and Ceramat® brands and from Deuteron GmbH under the Deuteron MK® brand.

[0160] The proportion of pigments and fillers in aqueous coating compositions can be described in a manner known per se by the pigment volume concentration (PVC), which is the ratio in percentage of the volume of pigments (VP) and fillers (VF) to the total volume of binder (VB), pigments (VP) and fillers (VF) in the dried coating film: PVC [%] = (VP + VF) x 100 / (VP + VF + VB).

[0161] When aqueous coating compositions are formulated as paints, they usually have a pigment volume concentration (PVC) of at least 5%, particularly at least 10%, and typically not more than 90%, particularly not more than 85%. In a preferred group of embodiments, the PVC does not exceed 60%, particularly not more than 50%, specifically in the range of 5 to 60% or 5 to 50%. However, the inventive effect of the polymer dispersion also appears in varnishes that typically have a pigment / filler content of less than 5% by weight, based on the varnish, and correspondingly have a PVC of less than 5%. In yet another group of embodiments, the PVC is in the range of more than 60 to 90%, particularly in the range of 65 to 85%.

[0162] According to one group of embodiments, the water-based coating compositions of the present invention are designed as paints containing white pigments, i.e., they contain at least one white pigment and optionally one or more fillers. As the white pigment, they particularly preferably contain titanium dioxide in rutile form, optionally in combination with one or more fillers. Particularly preferably, the coating compositions of the present invention contain a white pigment, preferably in rutile form, more particularly titanium dioxide, in combination with one or more fillers, such as chalk, talc, or a mixture thereof.

[0163] In another preferred group of embodiments, the water-based coating composition of the present invention is designed as a clearcoat or wood stain formulation. In contrast to paints, clearcoats are essentially free of pigments and fillers, while wood stains do not contain much filler, i.e., have less than 5% PVC.

[0164] According to a particular group of embodiments, the present invention also provides a method for treating a pulmonary arthritis, comprising: i) at least one aqueous polymer latex as defined above; ii) titanium dioxide pigment; and The present invention relates to a water-based coating composition (hereinafter also referred to as an aqueous coating composition) comprising:

[0165] According to a further particular group of embodiments, the present invention also relates to the use of an aqueous polymer latex as a binder in an aqueous coating composition containing titanium dioxide pigment.

[0166] In the aforementioned embodiment, the aqueous polymer latex is combined with a TiO pigment slurry or paste. The TiO concentration of the aqueous TiO pigment slurry or paste used to prepare the aqueous coating composition generally ranges from 30% to 85% by weight, often from 40% to 80% by weight, in each case based on the total weight of the aqueous TiO pigment slurry or paste. The titanium dioxide pigment used to prepare the aqueous dispersion of the pigment slurry or paste can be any TiO pigment conventionally used in coating compositions, particularly aqueous coating compositions. In many cases, TiO pigments are used, and TiO particles are preferably in the rutile form. In another preferred embodiment, the TiO particles can also be coated with, for example, aluminum, silicon, and zirconium compounds.

[0167] Generally, the weight ratio of polymer to titanium dioxide pigment is in the range of 0.1:5.0 to 5.0:0.1. Preferably, the weight ratio of polymer to titanium dioxide pigment is in the range of 0.5:5.0 to 5.0:0.5. Even more preferably, the weight ratio of polymer to titanium dioxide pigment is in the range of 0.5:3.0 to 3.0:0.5, especially in the range of 0.5:1.5 to 1.5:0.5.

[0168] 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.

[0169] Generally, the aqueous coating composition further comprises at least one additive selected from the group consisting of thickeners, defoamers, leveling agents, coalescing agents, biocides, wetting or dispersing agents, fillers, and coalescing agents.

[0170] The aqueous coating composition can be easily prepared by mixing the TiO pigment powder or an aqueous slurry or paste of the TiO pigment with the aqueous polymer latex of the present invention, preferably by applying shear to the mixture, for example, by using a solubilizer conventionally used to prepare water-based paints. It is also possible to prepare an aqueous slurry or paste of the TiO pigment and the aqueous polymer latex of the present invention, and then incorporate or mix it with the additional polymer latex of the present invention or any other polymer latex binder.

[0171] Aqueous dispersions of polymer composites can also be prepared by incorporating the aqueous polymer latex of the present invention as a binder or co-binder into the aqueous base formulation of a paint that already contains TiO2 pigment, for example by mixing the aqueous polymer latex of the present invention with a pigment formulation that already contains further additives conventionally used in paint formulations.

[0172] To stabilize the TiO2 pigment particles in the aqueous pigment slurry or paste, the mixing may optionally be carried out in the presence of additives conventionally used in aqueous pigment slurries or pastes, such as dispersants. Suitable dispersants include, but are not limited to, polyphosphates such as sodium, potassium, or ammonium polyphosphate, alkali metal and ammonium salts of homopolymers or copolymers of acrylic acid or maleic anhydride polymers, polyphosphonates such as sodium 1-hydroxyethane-1,1-diphosphonate, and naphthalene sulfonates, especially the sodium salts thereof.

[0173] The polymer concentration of the aqueous polymer latex used to prepare the aqueous dispersion of the polymer composite generally ranges from 10% to 70% by weight, preferably from 20% to 65% by weight, and most preferably from 30% to 60% by weight, in each case based on the total weight of the aqueous polymer latex.

[0174] In addition to the polymer latex and titanium dioxide pigment of the present invention and optional conventional binders, the aqueous coating composition may contain one or more pigments different from the TiO2 pigment and / or fillers as described above.

[0175] Preferably, the water-based coating composition comprises at least one aqueous polymer latex as defined herein and further comprises a rheology modifier. Suitable rheology modifiers include associative thickener polymers and non-associative rheology modifiers. The aqueous liquid composition preferably comprises a thickener selected from the group consisting of associative thickeners, non-associative thickeners, and combinations thereof.

[0176] Associative thickener polymers are well known and have been frequently described in the scientific literature, for example by EJ Schaller et al., "Associative Thickeners" in Handbook of Coating Additives, Vol. 2 (Editor LJ Calbo), Marcel Decker 192, pp. 105-164, J. Bieleman "PUR-Verdicker" in Additives for Coatings (Editor J. Bielemann), Wiley 2000, pp. 50-58. NiSAT thickener polymers of the HEUR and HMPE type are also described in the patent literature, for example in U.S. Pat. No. 4,079,028, U.S. Pat. No. 4,155,892, EP 61822, EP 307775, WO 96 / 31550, EP 612329, EP 1013264, EP 1541643, EP 1584331, EP 2184304, DE 4137247, DE 102004008015, DE 102004031786, U.S. Pat. Appl. No. 2011 / 0166291 and WO 2012 / 052508. Separately, associative thickener polymers are commercially available.

[0177] Associative thickener polymers include anionic acrylate-type thickener polymers, so-called HASE polymers (hydrophobically modified polyacrylate thickeners), which are copolymers of acrylic acid monomers and alkyl acrylate monomers, where the alkyl group of the alkyl acrylate ester can have 6 to 24 carbon atoms. Associative thickener polymers also include nonionic associative thickeners, 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 having at least four 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 oxides, also known as HMPEs.

[0178] The amount of associative thickener polymer will depend on the desired viscosity profile and will often range from 0.05 to 2.5%, especially 0.1 to 2%, and especially 0.2 to 2% by weight, based on the latex paint.

[0179] Suitable non-associative rheology modifiers are in particular cellulosic thickeners, especially hydroxyethyl cellulose, but also thickeners based on acrylate emulsions (ASE). Among the non-associative rheology modifiers, non-associative cellulosic thickeners are preferred.

[0180] The total amount of thickener polymer depends on the desired viscosity profile and is often in the range of 0.05 to 6%, especially 0.1 to 5.5%, and especially 0.15 to 5% by weight, based on the latex paint.

[0181] The aqueous coating composition of the present invention may also contain conventional auxiliaries, which, in a well-known manner, depend on the type of coating, wetting or dispersing agents, -Film-forming aids, also known as fusing agents, leveling agents, -UV stabilizers, biocides, and -Antifoaming / degassing agents These include, but are not limited to:

[0182] Suitable wetting or dispersing agents are, for example, sodium, potassium or ammonium polyphosphate, alkali metal and ammonium salts of acrylic acid copolymers or maleic anhydride copolymers, polyphosphonates, such as sodium 1-hydroxyethane-1,1-diphosphonate and naphthalenesulfonates, in particular their sodium salts.

[0183] Suitable coalescing aids are solvents and plasticizers. In contrast to solvents, plasticizers have low volatility and preferably have a boiling point at 1013 mbar above 250°C, while solvents have higher volatility than plasticizers and preferably have a boiling point at 1013 mbar below 250°C. Suitable coalescing aids include, for example, white spirit, pine oil, propylene glycol, ethylene glycol, butyl glycol, butyl glycol acetate, butyl glycol diacetate, butyl diglycol, butyl carbitol, 1-methoxy-2-propanol, 2,2,2-trimethyl-1,3-pentanediol monoisobutyrate (Texanol®), and glycol ethers and esters, such as those commercially available from BASF SE under the names Solvenon®, Lusolvan®, and Loxanol®, and from Dow under the trade name Dowanol®. The amount is preferably less than 5% by weight, more preferably less than 1% by weight, based on the total formulation. Formulation without coalescents is entirely possible. In many cases, the coating composition does not require any coalescents.

[0184] Further suitable auxiliaries 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.

[0185] The water-based coating composition of the present invention may 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 weight of the water-based coating composition. In the context of the present invention, volatile compounds are compounds having a boiling point of less than 250° C. at 1013 mbar.

[0186] The water-based coating compositions of the present invention are particularly useful for architectural coatings, i.e., for coating the exterior or interior of buildings, where the substrate may be a mineral substrate such as plaster, gypsum, plasterboard or concrete, wood, wood-based materials, metal, wallpaper, or plastic, e.g., PVC.

[0187] The water-based coating composition can be applied to the desired substrate in a conventional manner, for example, by brush or roller application, by spraying, by dipping, by rolling, or by bar coating. Preferred application is by brush and / or roller.

[0188] The coating of the substrate is usually carried out in such a way that the substrate is first coated with the aqueous coating composition of the invention and then the aqueous coating thus obtained is subjected to a drying step, in particular within a temperature range of from -10°C to +50°C, advantageously from +5°C to +40°C, particularly advantageously from +10°C to +35°C.

[0189] Substrates coated with the waterborne coating compositions of the present invention have excellent resistance to whitening upon exposure to water or weathering conditions. Additionally, the coatings have good adhesion properties, such as high dry alkyd adhesion, good opacity, high block resistance, good stain release properties, high humidity scrub resistance, and low stain adhesion. [Example]

[0190] The invention should now be illustrated by the following non-limiting examples.

[0191] 1. Abbreviation: MeHQ 4-Methoxyphenol (hydroquinone monomethyl ether) Weight% Weight%

[0192] In this specification and below, the terms "room temperature" and "ambient temperature" mean a temperature in the range of 22-23°C.

[0193] 2. Polymer Latex Analysis 2.1 Solids The solids content was determined by drying a defined 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. in a drying cabinet (2 hours). Two separate measurements were carried out. The values ​​reported in the examples are the average of the two measurements.

[0194] 2.2 Particle size Unless otherwise stated, the average particle size of the polymer latex was determined by dynamic light scattering (DLS) as described above using a Malvern HPPS.

[0195] 2.3 Glass transition temperature Tg The glass transition temperature was determined by the DSC method (differential scanning calorimetry, 20 K / min, midpoint measurement, DIN 53765:1994-03) on a DSC instrument (Q 2000 series from TA instruments).

[0196] 2.4 pH measurement pH measurements were performed on the reaction mixture using a pH meter.

[0197] 3. Ingredients In this example, the following components are used:

[0198] [Table 1A] [Table 1B]

[0199] Isobutyl acrylate can be prepared similarly to the protocol for producing bioisoamyl acrylate by transesterification of ethyl acrylate with isobutanol described in WO 2022 / 018013.

[0200] Protocol for Preparing Cyclopentyl Methacrylate To a heatable 4 L double-jacketed glass reactor equipped with a three-stage cross-arm stirrer, water remover, central condenser, heat element, and heatable cover equipped with lean air sparging, 1000 g of cyclopentanol was added.

[0201] 3.1 g of 12% sodium borohydride in 40% NaOH was added and stirred. After 2 hours, 0.89 g of MeHQ, 1098 g of glacial methacrylic acid, 47.8 g of 70% methanesulfonic acid, 0.24 g of copper(I) chloride, 1.18 g of 50% phosphinic acid, and 800 g of cyclohexane were added. The water remover was charged with cyclohexane.

[0202] The reaction mixture was heated to a bath temperature of 115°C while blowing air through it. The azeotrope of water and cyclohexane was distilled off at a sump temperature of 90-97°C. During the course of the reaction, an additional 600 g of cyclohexane was added. Within 8 hours, 214 g of water was distilled off, and the reaction was stopped by cooling to room temperature.

[0203] The reaction mixture was cooled and extracted successively with 2000 g of water, 1255 g of 6.5% NaOH solution and 2000 g of water. The aqueous phase was discarded.

[0204] 3280 g of product solution in cyclohexane were obtained, 0.3 g of MeHQ was added, and the solution was then concentrated in vacuo at 60° C. and 380 to 10 mbar.

[0205] Cyclopentyl methacrylate was obtained in a yield of 1528 g (85%) with a GC purity of 96.5 GC area %.

[0206] Protocol for Preparing Cyclopentyl Acrylate A 500 mL four-neck round-bottom flask equipped with a glass stirrer, a water remover with a powerful condenser, an air sparging tube, and a thermometer was charged with 100 g of cyclopentanol.

[0207] 0.31 g of a 12% solution of sodium borohydride in 40% NaOH was added and stirred. After 2 hours, 0.09 g of MeHQ, 91.9 g of glacial acrylic acid, 4.78 g of 70% methanesulfonic acid, 0.019 g of copper(I) chloride, 0.095 g of 50% phosphinic acid, and 40 g of cyclohexane were added. The water remover was charged with cyclohexane.

[0208] With an applied bath temperature of 115°C and sparging with air, the reaction mixture was heated to an internal temperature of 96°C, which increased to 121°C over the course of the reaction.

[0209] The azeotrope of water and cyclohexane was distilled off continuously. The aqueous phase was discarded and the organic phase was returned to the flask.

[0210] After distilling off 20 g of water, the reaction mixture was cooled to room temperature and the organic phase was extracted with 200 g of water, 25.8 g of 12.5% ​​NaOH and finally with 200 g of water.

[0211] 0.02 g of MeHQ was added and the cyclohexane was distilled off under vacuum.

[0212] 123.3 g of cyclopentyl acrylate was obtained with a GC area % purity of greater than 95.

[0213] 4. Preparation Example 4.1 Binder Example Invention Example E1 Binders based on polymers with cyclopentyl methacrylate and isobutyl acrylate A reactor equipped with a stirrer, temperature control, nitrogen inlet and several injection ports is charged with 244.3 g of deionized water, 27.3 g of polystyrene seed dispersion (33 wt %, particle size: 30 nm). The reaction mixture is purged with nitrogen and heated to 85°C. At 85°C, 5.0 g of Feed 2 is added. After 5 minutes, Feed 1 and Feed 2 are added over 180 minutes. 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% by weight solution in water), 291.1 g cyclopentyl methacrylate, 360.5 g isobutyl acrylate. Feed 2: 19.8 g of an aqueous solution of sodium persulfate (7% by weight). The reaction mixture is post-polymerized at 85° C. for 30 minutes.

[0214] Feed 3 and Feed 4 are then added over 60 minutes. Feed 3: 6.9 g of an aqueous solution of t-butyl hydroperoxide (10% by weight). Feed 4: 6.2 g of Rongalit C in water (10% by weight).

[0215] The reaction mixture is then cooled to ambient temperature and neutralized with sodium hydroxide to pH 8-9.

[0216] Tg (dry dispersion): 19℃ Average particle size: 136 nm Solid content: 47.4% by weight

[0217] Invention Example E2 Binder based on a polymer with cyclopentyl methacrylate, isobutyl acrylate and methyl methacrylate A reactor equipped with a stirrer, temperature control, nitrogen inlet and several injection ports is charged with 244.3 g of deionized water, 27.3 g of polystyrene seed dispersion (33 wt %, particle size: 30 nm). The reaction mixture is purged with nitrogen and heated to 85°C. At 85°C, 5.0 g of Feed 2 is added. After 5 minutes, Feed 1 and Feed 2 are added over 180 minutes. 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% by weight solution in water), 149.0 g cyclopentyl methacrylate, 149.0 g methyl methacrylate, 381.0 g isobutyl acrylate. Feed 2: 19.8 g of an aqueous solution of sodium persulfate (7% by weight). The reaction mixture is post-polymerized at 85° C. for 30 minutes.

[0218] Feed 3 and Feed 4 are then added over 60 minutes. Feed 3: 6.9 g of an aqueous solution of t-butyl hydroperoxide (10% by weight). Feed 4: 6.2 g of Rongalit C in water (10% by weight).

[0219] The reaction mixture is then cooled to ambient temperature and neutralized with sodium hydroxide to pH 8-9.

[0220] Tg (dry dispersion): 21℃ Average particle size: 124 nm Solid content: 48.4% by weight

[0221] Comparative Example C1 Binders based on polymers with n-butyl acrylate and styrene A reactor equipped with a stirrer, temperature control, nitrogen inlet and several injection ports is charged with 244.3 g of deionized water, 27.3 g of polystyrene seed dispersion (33 wt %, particle size: 30 nm). The reaction mixture is purged with nitrogen and heated to 85°C. At 85°C, 5.0 g of Feed 2 is added. After 5 minutes, Feed 1 and Feed 2 are added over 180 minutes. 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), 318.8 g styrene, 360.4 g n-butyl acrylate. Feed 2: 19.8 g of an aqueous solution of sodium persulfate (7% by weight). The reaction mixture is post-polymerized at 85° C. for 30 minutes.

[0222] Feed 3 and Feed 4 are then added over 60 minutes. Feed 3: 6.9 g of an aqueous solution of t-butyl hydroperoxide (10% by weight). Feed 4: 6.2 g of Rongalit C in water (10% by weight).

[0223] The reaction mixture is then cooled to ambient temperature and neutralized with sodium hydroxide to pH 8-9.

[0224] Tg (dry dispersion): 18℃ Average particle size: 132 nm Solid content: 48.1% by weight

[0225] Comparative Example C2 Binders based on polymers with n-butyl acrylate and methyl methacrylate A reactor equipped with a stirrer, temperature control, nitrogen inlet and several injection ports is charged with 244.3 g of deionized water, 27.3 g of polystyrene seed dispersion (33 wt %, particle size: 30 nm). The reaction mixture is purged with nitrogen and heated to 85°C. At 85°C, 5.0 g of Feed 2 is added. After 5 minutes, Feed 1 and Feed 2 are added over 180 minutes. 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% by weight solution in water), 349.0 g methyl methacrylate, 335.0 g n-butyl acrylate. Feed 2: 19.8 g of an aqueous solution of sodium persulfate (7% by weight). The reaction mixture is post-polymerized at 85° C. for 30 minutes.

[0226] Feed 3 and Feed 4 are then added over 60 minutes. Feed 3: 6.9 g of an aqueous solution of t-butyl hydroperoxide (10% by weight). Feed 4: 6.2 g of Rongalit C in water (10% by weight).

[0227] The reaction mixture is then cooled to ambient temperature and neutralized with sodium hydroxide to pH 8-9.

[0228] Tg (dry dispersion): 18℃ Average particle size: 138 nm Solid content: 48.8% by weight

[0229] Invention Example E3 Binder based on a polymer with cyclopentyl methacrylate, n-butyl acrylate and methyl methacrylate An emulsion was prepared by mixing 238.7 g of deionized water, 7.3 g of emulsifier 1, 22.0 g of emulsifier 2, and the respective amounts of monomers shown in the table below:

[0230] [Table 2]

[0231] An initiator solution was prepared by dissolving 0.7 g of sodium persulfate in 8.8 g of deionized water.

[0232] Oxidizing solution O was prepared by dissolving 0.3 g of t-butyl hydroperoxide in 3 g of deionized water.

[0233] Reducing solution R was prepared by dissolving 0.45 g of sodium sulfite in 3.6 g of deionized water mixed with 0.2 g of acetone.

[0234] A reaction vessel equipped with a stirrer and three separate feed lines was charged with 166 g of deionized water and 5.8 g of seed latex, and the vessel was preheated to 95°C. After reaching a temperature of 95°C, the emulsion was fed into the reaction vessel over 165 minutes while maintaining the temperature at 95°C. Starting simultaneously with the emulsion, the initiator solution was fed into the reaction vessel over 165 minutes via a separate feed line. After addition of the emulsion and initiator solution was complete, stirring was continued for an additional 15 minutes at 95°C. Oxidizing solution O and reducing solution R were then fed in parallel to the reaction vessel over 60 minutes at 95°C via separate feed lines. After addition of the oxidizing and reducing solutions was complete, the vessel was cooled to room temperature, and 7.3 g of sodium hydroxide solution (10 wt.%) was added. aq ) was added.

[0235] Emulsifier 1: 45% by weight aqueous solution of the sodium salt of C12-alkyldiphenyloxide disulfonate 20 wt% aqueous solution of ethoxylated iso-C13 alkanol with emulsifier 2:8 EO Seed latex: polystyrene latex with a solids content of 33 wt% and a diameter of 30 nm

[0236] Tg (dry dispersion): -1.3℃ Average particle size: 196 nm Solid content: 49.2% by weight

[0237] Invention Example E4 Binder based on a polymer with cyclopentyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and styrene An emulsion was prepared by mixing 209 g of deionized water, 39.3 g of Emulsifier 3, and the amounts of each of the monomers shown in the table below:

[0238] [Table 3]

[0239] An initiator solution was prepared by dissolving 2.2 g of sodium persulfate in 29.2 g of deionized water.

[0240] Oxidizing solution O was prepared by dissolving 1.7 g of t-butyl hydroperoxide in 14.8 g of deionized water.

[0241] Reducing solution R was prepared by dissolving 1.5 g of sodium sulfite in 11.7 g of deionized water mixed with 0.7 g of acetone.

[0242] A reaction vessel equipped with a stirrer and three separate feed lines was charged with 163 g of deionized water and 9.2 g of seed latex, and the vessel was preheated to 85°C. After reaching a temperature of 85°C, the emulsion was fed into the reaction vessel over 150 minutes while maintaining the temperature at 85°C. Starting simultaneously with the emulsion, the initiator solution was fed into the reaction vessel via a separate feed line over 180 minutes. After addition of the emulsion and initiator solution was complete, stirring was continued for an additional 30 minutes at 85°C. Oxidizing solution O and reducing solution R were then fed in parallel to the reaction vessel over 120 minutes at 85°C via separate feed lines. After addition of the oxidizing and reducing solutions was complete, the vessel was cooled to room temperature, and 29.2 g of sodium hydroxide solution (10 wt.%) was added. aq ) was added.

[0243] Emulsifier 3: 27% by weight aqueous solution of sodium lauryl ether sulfate Seed latex: polystyrene latex with a solids content of 33 wt% and a diameter of 30 nm

[0244] Tg (dry dispersion): 5℃ Average particle size: 159 nm Solid content: 50.7% by weight

[0245] Comparative Example C3 Binders based on polymers with methyl methacrylate and n-butyl acrylate An emulsion was prepared by mixing 238.7 g of deionized water, 7.3 g of emulsifier 1, 22.0 g of emulsifier 2, and the respective amounts of monomers shown in the table below:

[0246] [Table 4]

[0247] An initiator solution was prepared by dissolving 0.7 g of sodium persulfate in 8.8 g of deionized water.

[0248] Oxidizing solution O was prepared by dissolving 0.3 g of t-butyl hydroperoxide in 3 g of deionized water.

[0249] Reducing solution R was prepared by dissolving 0.45 g of sodium sulfite in 3.6 g of deionized water mixed with 0.2 g of acetone.

[0250] A reaction vessel equipped with a stirrer and three separate feed lines was charged with 166 g of deionized water and 5.8 g of seed latex, and the vessel was preheated to 95°C. After reaching a temperature of 95°C, the emulsion was fed into the reaction vessel over 165 minutes while maintaining the temperature at 95°C. Starting simultaneously with the emulsion, the initiator solution was fed into the reaction vessel over 165 minutes via a separate feed line. After addition of the emulsion and initiator solution was complete, stirring was continued for an additional 15 minutes at 95°C. Oxidizing solution O and reducing solution R were then fed in parallel to the reaction vessel over 60 minutes at 95°C via separate feed lines. After addition of the oxidizing and reducing solutions was complete, the vessel was cooled to room temperature, and 7.3 g of sodium hydroxide solution (10 wt.%) was added. aq ) was added.

[0251] Emulsifier 1: 45% by weight aqueous solution of the sodium salt of C12-alkyldiphenyloxide disulfonate 20 wt% aqueous solution of ethoxylated iso-C13 alkanol with emulsifier 2:8 EO Seed latex: polystyrene latex with a solids content of 33 wt% and a diameter of 30 nm

[0252] Tg (dry dispersion): 8℃ Average particle size: 193 nm Solid content: 52.5% by weight

[0253] Comparative example C4 Binder based on a polymer with styrene, n-butyl acrylate and 2-ethylhexyl acrylate An emulsion was prepared by mixing 209 g of deionized water, 39.3 g of Emulsifier 3, and the amounts of each of the monomers shown in the table below:

[0254] [Table 5]

[0255] An initiator solution was prepared by dissolving 2.2 g of sodium persulfate in 29.2 g of deionized water.

[0256] Oxidizing solution O was prepared by dissolving 1.7 g of t-butyl hydroperoxide in 14.8 g of deionized water.

[0257] Reducing solution R was prepared by dissolving 1.5 g of sodium sulfite in 11.7 g of deionized water mixed with 0.7 g of acetone.

[0258] A reaction vessel equipped with a stirrer and three separate feed lines was charged with 163 g of deionized water and 9.2 g of seed latex, and the vessel was preheated to 85°C. After reaching a temperature of 85°C, the emulsion was fed into the reaction vessel over 150 minutes while maintaining the temperature at 85°C. Starting simultaneously with the emulsion, the initiator solution was fed into the reaction vessel via a separate feed line over 180 minutes. After addition of the emulsion and initiator solution was complete, stirring was continued for an additional 30 minutes at 85°C. Oxidizing solution O and reducing solution R were then fed in parallel to the reaction vessel over 120 minutes at 85°C via separate feed lines. After addition of the oxidizing and reducing solutions was complete, the vessel was cooled to room temperature, and 29.2 g of sodium hydroxide solution (10 wt.%) was added. aq ) was added.

[0259] Emulsifier 3: 27% by weight aqueous solution of sodium lauryl ether sulfate Seed latex: polystyrene latex with a solids content of 33 wt% and a diameter of 30 nm

[0260] Tg (dry dispersion): 8℃ Average particle size: 165 nm Solid content: 51.8% by weight

[0261] 4.2 Formulation example Invention Example E5 Semi-gloss paint formulation containing binder of Example E1 200.0 g of Kronos 4311 pigment was mixed with 15.0 g of water. At low agitation speed, 1.0 g of AMP-95 neutralizer (Angus Chemical Company), 1.0 g of BYK-022 antifoam (BYK), 10.0 g of Tamol 731 A dispersant (Dow), and 3.0 g of Hydropalat WE 3320 wetting agent (BASF) were added. At high agitation speed, 1.5 g of Attagel 50 (BASF), 25.0 g of Minex 10 (Sibelco) filler, 125.0 g of Kronos 4311 pigment, 2.0 g of Proxel AQ, 20.0 g of Aquaflow NHS-310 (Ashland) nonionic associative thickener, and 100.1 g of water were added and mixed for 30 minutes. The mixture is filtered through a 400 μm filter and then added to a combination of 502.0 g of binder from Example E1, 25.0 g of Ropaque Ultra E polymer pigment (Dow), and 1.5 g of Tego Foamex 810 defoamer (Evonik) and stirred for 5 minutes. 11.0 g of Texanol coalescent (Eastman) is added and stirred for 5 minutes. 3.0 g of Polyphase 663 fungicide (Troy Corporation) and 1.0 g of Rheolate CVS 10 nonionic associative thickener (Elementis) are then added and mixed for 5 minutes. Finally, 1.5 g of Acrysol RM 895 nonionic associative thickener (Dow) and 5.4 g of water are added, and the mixture is stirred at medium speed for 30 minutes.

[0262] Invention Example E6 Semi-gloss paint formulation containing binder of Example E2 200.0 g of Kronos 4311 pigment was mixed with 15.0 g of water. At low agitation speed, 1.75 g of AMP-95 neutralizer (Angus Chemical Company), 5.0 g of propylene glycol (Univar), 2.0 g of Foamstar 2420 defoamer (BASF), 10.0 g of Tamol 165 A dispersant (Dow), and 3.0 g of Hydropalat WE 3320 wetting agent (BASF) were added. At high agitation speed, 1.5 g of Attagel 50 (BASF), 25.0 g of Minex 10 (Sibelco) filler, 125.0 g of Kronos 4311 pigment, 101.4 g of water, and 20.0 g of Aquaflow NHS-310 (Ashland) nonionic associative thickener were added and mixed for 30 minutes. The mixture was filtered through a 400 μm filter and then added to a combination of 496.8 g of binder from Example E2, 25.0 g of Ropaque Ultra E polymer pigment (Dow), and 2.0 g of Foamstar 2420 defoamer (BASF) and stirred for 5 minutes. 9.0 g of Texanol coalescent (Eastman) and 8.4 g of Optifilm 400 coalescent (Eastman) were added and mixed for 5 minutes. 2.0 g of Proxel AQ biocide (Lonza), 3.0 g of Polyphase 663 fungicide (Troy Corporation), and 2.5 g of Rheolate CVS 10 nonionic associative thickener (Elementis) were then added and mixed for 5 minutes. Finally, 1.5 g of Acrysol RM 895 nonionic associative thickener (Dow) was added, and the mixture was stirred at medium speed for 30 minutes.

[0263] Comparative example C5 Semi-gloss paint formulation containing binder of Example C1 200.0 g of Kronos 4311 pigment was mixed with 15.0 g of water. At low agitation speed, 1.0 g of AMP-95 neutralizer (Angus Chemical Company), 1.0 g of BYK-022 antifoam (BYK), 10.0 g of Tamol 731 A dispersant (Dow), and 3.0 g of Hydropalat WE 3320 wetting agent (BASF) were added. At high agitation speed, 1.5 g of Attagel 50 (BASF), 25.0 g of Minex 10 (Sibelco) filler, 125.0 g of Kronos 4311 pigment, 2.0 g of Proxel AQ, 20.0 g of Aquaflow NHS-310 (Ashland) nonionic associative thickener, and 98.0 g of water were added and mixed for 30 minutes. The mixture is filtered through a 400 μm filter and then added to a combination of 500.0 g of binder from Example C1, 25.0 g of Ropaque Ultra E polymer pigment (Dow), and 1.5 g of Tego Foamex 810 defoamer (Evonik) and stirred for 5 minutes. 12.0 g of Texanol coalescent (Eastman) is added and mixed for 5 minutes. 3.0 g of Polyphase 663 fungicide (Troy Corporation) and 1.0 g of Rheolate CVS 10 nonionic associative thickener (Elementis) are then added and mixed for 5 minutes. Finally, 1.5 g of Acrysol RM 895 nonionic associative thickener (Dow) and 4.3 g of water are added, and the mixture is stirred at medium speed for 30 minutes.

[0264] Comparative example C6 Semi-gloss paint formulation containing binder of Example C2 200.0 g of Kronos 4311 pigment was mixed with 15.0 g of water. At low agitation speed, 1.75 g of AMP-95 neutralizer (Angus Chemical Company), 5.0 g of propylene glycol (Univar), 2.0 g of Foamstar 2420 defoamer (BASF), 10.0 g of Tamol 165 A dispersant (Dow), and 3.0 g of Hydropalat WE 3320 wetting agent (BASF) were added. At high agitation speed, 1.5 g of Attagel 50 (BASF), 25.0 g of Minex 10 (Sibelco) filler, 125.0 g of Kronos 4311 pigment, 109.0 g of water, and 20.0 g of Aquaflow NHS-310 (Ashland) nonionic associative thickener were added and mixed for 30 minutes. The mixture was filtered through a 400 μm filter and then added to a combination of 495.8 g of binder from Example C2, 25.0 g of Ropaque Ultra E polymer pigment (Dow), and 2.0 g of Foamstar 2420 defoamer (BASF) and stirred for 5 minutes. 9.0 g of Texanol coalescent (Eastman) and 5.8 g of Optifilm 400 coalescent (Eastman) were added and mixed for 5 minutes. 2.0 g of Proxel AQ biocide (Lonza), 3.0 g of Polyphase 663 fungicide (Troy Corporation), and 4.0 g of Rheolate CVS 10 nonionic associative thickener (Elementis) were then added and mixed for 5 minutes. Finally, 2.5 g of Acrysol RM 895 nonionic associative thickener (Dow) was added, and the mixture was stirred at medium speed for 30 minutes.

[0265] Invention Example E7 Paint formulation containing binder from Example E3

[0266] [Table 6]

[0267] Comparative Example C7 Paint formulation containing binder from Example C5

[0268] [Table 7]

[0269] Invention Example E8 Paint formulation containing binder from Example E4

[0270] [Table 8]

[0271] Comparative Example C8 Semi-gloss paint formulation containing binder of Example C4 [Table 9]

[0272] 4.3 Coating characteristics The following coating properties were determined: Gloss: Films were prepared on Leneta 3B black and white shielded drawdown cards using a 3 mil drawdown bar. Films were allowed to dry at room temperature for 24 hours. Gloss was measured at angles of 20°, 60°, and 80° using a glossmeter. The results were as follows:

[0273] [Table 10]

[0274] Gloss is improved in E6 compared to C6

[0275] Low shear viscosity: The low shear viscosity was measured according to ASTM D562 seven days after preparation, with the following results:

[0276] [Table 11]

[0277] High shear viscosity: High shear viscosity measured according to ASTM D4287 7 days after preparation. The results were as follows:

[0278] [Table 12]

[0279] Thickening efficiency is improved in E6 compared to C6

[0280] Opacity: Films were prepared on Leneta 3B black and white shielded drawdown cards using a 3 mil drawdown bar. Films were allowed to dry at room temperature for 24 hours. Opacity was determined spectrophotometrically as the ratio of light reflected from the dried coating on the black and white sections of the Leneta card. Opacity indicates the ability of the coating to conceal a black surface. Results were as follows:

[0281] [Table 13]

[0282] Dry Alkyd Adhesion: Dry alkyd adhesion was measured according to ASTM D3359. Evaluations were performed after 7 days. Dry alkyd adhesion was rated on a scale of 0 to 5, with 0 = complete removal and 5 = no removal. The results were as follows: [Table 14]

[0283] Dry alkyd adhesion is improved for E6 compared to C6, and E5 compared to C5.

[0284] Block resistance: Block resistance of E5 and C5 was measured at room temperature according to ASTM D4946. Evaluations were performed after 7 days. Block resistance was rated on a scale of 0 to 10, with a mark of 1 equaling over 90% seal and a mark of 10 equaling no tack.

[0285] The results were as follows: E5:9, C5:9.

[0286] Block resistance is comparable for E5 and C5.

[0287] Stain removal: Stain removal was measured according to ASTM D4828. The results for coatings from E5 and E6 were comparable to those from C5 and C6 for pencil, lipstick, crayon, ballpoint pen, red wine, ketchup, coffee, and mustard (visual inspection), respectively.

[0288] Dirt adhesion: The mille glaze on the yellow pine wood surface is rubbed with water and allowed to dry overnight. The substrate is divided into sections depending on the number of samples to be tested. Using an appropriate brush, the test paint sample is applied at its natural spreading rate. The coating is allowed to cure at room temperature for 4 and 24 hours, respectively. Half of the coated area is then covered with 2 inches of dry soil (Arizona soil or carpet soil). The panel is allowed to stand for 15 minutes, then tilted vertically and tapped to remove the soil. The soiled area of ​​each sample is lightly brushed (15 strokes).

[0289] The stain adhesion is equivalent between E5, C5 and E6, C6 (visual evaluation).

[0290] Moisture scrub resistance: The wet scrub resistance (WSR) of the prepared latex paints was tested by the nonwoven pad method according to ISO 11998. WSR is evaluated based on the weight loss per unit area caused by abrasion and calculated back to the average thickness loss given in μm.

[0291] [Table 15]

[0292] WSW is equivalent for E7, C7 and E8, C8.

[0293] Spreading rate: The opacity, which is the hiding power, was quantified by diffusivity measurements. These measurements were carried out by applying different film thicknesses onto a defined contrast paper, e.g., a Renata foil with black and white areas, using a drawdown bar, i.e., a doctor blade (e.g., 150, 200, 220, and 250 μm wet), and then measuring the contrast ratio. The value is then calculated as the reciprocal of the volume of paint per area [m ] required to cover the substrate with a given contrast ratio, e.g., 98% or 99.5%, according to ISO DIN 13300. 2 / L] (the reciprocal of the membrane thickness) is interpolated to yield the so-called diffusivity.

[0294] [Table 16]

[0295] Diffusion rates are improved in E7 compared to C7 and in E8 compared to C8.

Claims

1. 1. An aqueous polymer latex of a film-forming copolymer obtained by aqueous emulsion polymerization of ethylenically unsaturated monomers M, - 5 to 70% by weight, based on the total amount of monomers M, of at least one monomer M1 chosen from cyclopentyl acrylate, cyclopentyl methacrylate and mixtures thereof; - 20 to 90% by weight of C of acrylic acid, excluding tert-butyl acrylate, based on the total amount of monomers M ２ -C ２０ - alkyl esters, and C of methacrylic acid ５ -C ２０ at least one monomer M2 chosen from alkyl esters, as well as mixtures thereof, - 0 to 40% by weight of tert.-butyl acrylate, methacrylic acid C, based on the total amount of monomers M １ -C ４ one or more monomers M3 chosen from alkyl esters, cyclohexyl methacrylate, isobornyl methacrylate and monovinyl aromatic monomers, and mixtures thereof; wherein the total amount of monomers M1 and M3 ranges from 5 to 70% by weight, based on the total amount of ethylenically unsaturated monomers M, and the total amount of monomers M1, M2 and M3 is at least 85% by weight, based on the total amount of ethylenically unsaturated monomers M, Water-based polymer latex.

2. 2. The aqueous polymer latex of claim 1, wherein the monomer M1 is cyclopentyl methacrylate.

3. 3. The aqueous polymer latex according to claim 1, wherein at least the carbon atom of the cyclopentyl group in said monomer M1 is of biological origin.

4. 4. The aqueous polymer latex of claim 1, wherein the monomer M2 comprises isobutyl acrylate.

5. 5. The aqueous polymer latex of claim 4, wherein at least the carbon atoms of the isobutyl group of said isobutyl acrylate are of biological origin.

6. 6. The aqueous polymer latex according to claim 4 or 5, wherein the amount of isobutyl acrylate ranges from 20 to 80% by weight, based on the total amount of monomers M.

7. 7. The aqueous polymer latex of claim 1, wherein the monomer M3 comprises or is methyl methacrylate, or the monomer M3 comprises or is styrene.

8. 8. The aqueous polymer latex according to claim 1, wherein the monomers M further comprise at least one monomer M4 selected from monoethylenically unsaturated monomers having an acidic group.

9. 9. The aqueous polymer latex of claim 8, wherein the monomer M4 is selected from acrylic acid, methacrylic acid, itaconic acid, and combinations thereof.

10. 10. The aqueous polymer latex according to claim 1, wherein the monomers M further comprise at least one monoethylenically unsaturated nonionic monomer M5 having a solubility in deionized water of at least 60 g / L at 20°C and 1 bar.

11. The monomer M is i. 5 to 70 wt. % of cyclopentyl methacrylate as monomer M1, based on the total amount of monomers M; ii. 20 to 90 wt. % of at least one monomer M2, based on the total amount of monomers M, comprising or being isobutyl acrylate, or comprising or being n-butyl acrylate; iii. 0 to 40 wt. % of at least one monomer M3 selected from styrene, methyl methacrylate, and combinations thereof, based on the total amount of monomers M; iv. 0.05 to 5 wt. % of one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having an acidic group, based on the total amount of monomers M; v. 0 to 9.95 wt. %, based on the total weight of the monomers M, of one or more nonionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20° C. and 1 bar; The aqueous polymer latex according to any one of claims 1 to 10, comprising:

12. 12. The aqueous polymer latex according to any one of claims 1 to 11, wherein the polymer particles comprise a polymer phase having a glass transition temperature Tg in the range of -25 to +40°C.

13. 13. A process for producing the aqueous polymer latex of any one of claims 1 to 12, comprising carrying out aqueous emulsion polymerization of said monomers M.

14. 13. Use of the aqueous polymer latex according to any one of claims 1 to 12 as a binder in a water-based coating composition.

15. 1. A water-based coating composition comprising: c) a binder polymer in the form of an aqueous polymer latex according to any one of claims 1 to 12; d) at least one further component conventionally used in water-based coating compositions which is not a binder; A water-based coating composition comprising:

16. 16. The coating composition of claim 15, which is a latex paint, in particular a latex paint for architectural coatings, a wood coating or wood staining composition, or a latex paint for interior coatings.

Images