Aqueous polymer latex copolymer suitable as a binder in water-based coating compositions

Abstract

Thus, the present invention relates to an aqueous polymer latex of a copolymer obtained by aqueous emulsion polymerization of an ethylenically unsaturated monomer M, iv. 5 to 90% by weight, in particular 10 to 70% by weight, in particular 10 to 50% by weight, based on the total amount of monomer M, of monomer M1 which is 1-heptyl acrylate, v. 0 to 70% by weight, based on the total amount of monomer M, of C2-C6-alkyl esters of acrylic acid excluding tert-butyl acrylate, C8-C 20 -alkyl esters of acrylic acid and C5-C 20 -alkyl esters of methacrylic acid, and at least one monomer M2 selected from mixtures thereof, vi. 5 to 70% by weight, based on the total amount of monomer M, of tert-butyl acrylate, C1-C4-alkyl esters of methacrylic acid, C5-C 20 -cycloalkyl esters of acrylic acid, C5-C 20 -cycloalkyl esters of methacrylic acid, C5-C 20 -cycloalkylmethyl esters of acrylic acid, C5-C 20 -cycloalkylmethyl esters of methacrylic acid (the cycloalkyl in the above monomers is monocyclic, bicyclic or tricyclic, one or two non-adjacent CH2 moieties of the cycloalkyl may be replaced by oxygen atoms, the cycloalkyl may be unsubstituted or may have 1, 2, 3 or 4 methyl groups), and at least one monomer M3 selected from monovinyl aromatic monomers, methylene-gamma-butyrolactone, and mixtures thereof, comprising, where the total amount of monomers M1 and M2 ranges from 10 to 90% by weight based on the total amount of ethylenically unsaturated monomer M, and the total amount of monomers M1, M2 and M3 is at least 90% by weight based on the total amount of ethylenically unsaturated monomer M, relates to an aqueous polymer latex. The present invention also relates to a process for producing the aqueous polymer latex of the present invention. The present invention also relates to the use of these polymer latexes as binders in aqueous coating compositions and aqueous adhesive compositions, particularly as binders in aqueous coating compositions.

Description

[Technical Field]

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

[0002] Polymer latex, also known as polymer dispersion, is commonly known as a binder component, also called a binder or co-binder, particularly for coating compositions. As a binder or co-binder in a coating composition, one of the important requirements is that they provide hardness and adhesion of the coating to the coating surface. Furthermore, polymer latex must provide good opacity, good moisture scrubability, good dirt removal properties, low dirt adhesion, and low water absorption.

[0003] Despite advancements in many respects, providing polymer dispersions with a balanced coating profile remains a challenging task, as both coating properties and the stability of the polymer dispersion must be considered. In particular, harmonizing different coating property requirements simultaneously through binders is difficult. Generally, attempts to improve one property of the coating by changing the polymer composition of the binder significantly degrade other properties of the coating.

[0004] The polymer dispersions described in this art have certain advantages in one or more embodiments, but they do not necessarily have a well-balanced coating profile. Apart from that, they are based solely on monomers prepared from fossil sources. Given the ongoing discussion regarding the impact of CO2 emissions, there is a need to reduce fossil carbon in polymer latex. The term "bio-based" means that the monomers are prepared at least partially from renewable raw materials, such as plants, plant parts, plant waste, biomass, etc. These products are referred to as bio-based. 14 These materials are characterized by having a traceable content of carbon C. These materials can also be converted into suitable feedstocks, such as bionaphtha, as described, for example, in European Patent Application Publication No. 2290045 or European Patent Application Publication No. 2290034. Such feedstocks typically enter a chemical manufacturing system, such as a steam cracker, 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 by a mass balance scheme.

[0005] International Publication No. 2014 / 207389 describes the use of 2-octyl acrylate from renewable resources in the manufacture of polymer latex. Polymer latex is proposed as a binder.

[0006] International Publication No. 2022 / 018013 describes 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 thereby result in coatings with improved coating properties, such as whitening resistance, water absorption, and flexibility. Isobutyl acrylate and isoamyl acrylate can be obtained from biological sources—at least with respect to their alkanol portions—and thus allow for a reduction of fossil carbon in polymer latex.

[0007] Nevertheless, there remains a need to provide polymer latexes that are at least partially based on bio-based monomers and have an acceptable or improved coating profile that makes them suitable as binders in aqueous coating compositions, particularly for external and internal applications. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] European Patent Application Publication No. 2290045 [Patent Document 2] European Patent Application Publication No. 2290034 [Patent Document 3] International Publication No. 2014 / 207389 [Patent Document 4] International Publication No. 2022 / 018013 [Overview of the project] [Means for solving the problem]

[0009] Surprisingly, polymer latex based on a certain amount of 1-heptyl acrylate, hereafter monomer M1, in combination with other conventional or bio-based monomers M2 and M3 as defined herein, has been found to improve coating compositions, particularly the coating properties of the coating compositions, namely hardness, gloss, diffusivity (opacity), adhesion to coated surfaces, especially adhesion of the coating to surfaces pre-coated with alkyd resins (alkyd adhesion), scrub resistance, and reduction of dirt adhesion. Furthermore, 1-heptyl acrylate can be obtained from biological sources, at least with respect to its alkanol portion, thus enabling a reduction of fossil carbon in polymer latex. In particular, the combination of 1-heptyl acrylate and isobutyl acrylate is especially suitable for achieving the above-mentioned advantages and enabling the replacement of conventional acrylate monomers with bio-based monomers.

[0010] Therefore, the present invention relates to an aqueous polymer latex of a copolymer obtained by aqueous emulsion polymerization of an ethylenically unsaturated monomer M, i. Based on the total amount of monomer M, monomer M1 is 1-heptyl acrylate in an amount of 5 to 90% by weight, particularly 10 to 70% by weight, particularly 10 to 50% by weight, ii. Based on the total amount of monomer M, 0 to 70% by weight of C2-C6 alkyl esters of acrylic acid, excluding tert-butyl acrylate, and C8-C alkyl esters of acrylic acid. 20 - C5-C alkyl esters and methacrylic acid 20 -Alkyl esters, and at least one monomer M2 selected from mixtures thereof, iii. Based on the total amount of monomer M, 5 to 70% by weight of tert-butyl acrylate, C1-C4 alkyl ester of methacrylic acid, and C5-C of acrylic acid. 20 -Cycloalkyl ester, C5-C methacrylic acid 20 -Cycloalkyl esters, C5-C acrylic acid 20 -Cycloalkylmethyl ester, C5-C methacrylic acid 20-Cycloalkylmethyl ester (the cycloalkyl in the above monomer is monocyclic, bicyclic, or tricyclic, and one or two non-adjacent CH2 moieties of the cycloalkyl may be replaced with oxygen atoms, the cycloalkyl may be unsubstituted, or may have one, two, three, or four methyl groups), and at least one monomer M3 selected from monovinyl aromatic monomers, methylene-gamma-butyrolactone, and mixtures thereof, The present invention relates to an aqueous polymer latex in which the total amount of monomers M1 and M2 is in the range of 10 to 90% by weight, based on the total amount of ethylenically unsaturated monomer M, and the total amount of monomers M1, M2, and M3 is at least 90% by weight, based on the total amount of ethylenically unsaturated monomer M.

[0011] The present invention also relates to a process for producing the aqueous polymer latex of the present invention. This process comprises carrying out aqueous emulsion polymerization of monomer M.

[0012] The present invention also relates to the use of these polymer latexes as binders in aqueous coating compositions and aqueous adhesive compositions, particularly as binders in aqueous coating compositions.

[0013] Furthermore, the present invention is a) A binder polymer in the form of an aqueous polymer latex as defined herein, b) A water-based coating composition comprising at least one additional component that is not a binder and has been conventionally used in such compositions, This relates to an aqueous coating composition containing [a specific ingredient].

[0014] The present invention relates to several advantages.

[0015] Polymer latex is stable and provides a good and balanced coating profile for water-based coating compositions, such as improved hardness, improved adhesion properties, such as high wet and dry alkyd adhesion, low stain adhesion, improved scrub resistance, and good opacity.

[0016] The polymer latex contains a significant amount of monomers M1, M2, and M3 that can be obtained from bio-renewable resources, at least with respect to monomer M1 and also in part with respect to monomers M2 and M3. Therefore, they enable a significant reduction in the need for fossil carbon, especially at least 10%, particularly at least 25%, or even at least 40%, up to 100%. The incorporation of bio-carbon and the reduction of fossil carbon can reduce the carbon footprint of the polymer latex.

[0017] Due to their balanced application profiles, the polymer latexes are particularly useful as binders in aqueous architectural coatings and have beneficial properties in both aqueous primer and aqueous topcoat formulations, as well as in both exterior and interior architectural paints.

[0018] Here and throughout this specification, the term "bio-based monomer" means that each monomer is at least partially manufactured from molecules obtained from bio-renewable resources, such as biomass. Such molecules are characterized by a bio-carbon content of at least 90 mol%, preferably at least 95 mol%, for example 100 mol%, based on the total amount of carbon atoms in each molecule, such as by 1-heptanol or isobutanol.

[0019] The term "bio-carbon" indicates that the carbon is of biological origin and is derived from biomaterials / renewable resources. Here and hereinafter, renewable sources and bio-renewable sources are used synonymously and refer to sources of biological origin other than fossil sources. The bio-carbon content and the biomaterial content are expressions that indicate the same value. Materials of renewable origin or biomaterials are organic materials in which the carbon is derived from CO2 that was recently fixed (on a human scale) by photosynthesis from the atmosphere. Biomaterials (100% natural origin carbon) have an isotope ratio greater than 10 -12 greater, typically about 1.2×10 -12 of the isotope ratio14 C / 12 Although it contains C, fossil materials have a zero ratio. In fact, isotopes 14 C is formed in the atmosphere and integrated through photosynthesis over timescales of up to several decades. 14 The half-life of 1C is 5,730 years. Therefore, materials derived from photosynthesis, i.e., plants in general, are necessarily isotopes. 14 It has the maximum content in C. The content of biomaterials or biocarbons can be determined according to standard ASTM D 6866-12, method B (ASTM D 6866-06) and ASTM D 7026 (ASTM D 7026-04).

[0020] 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.

[0021] Here, and throughout this specification, the terms “water-based coating composition” and “water-based adhesive composition” mean a liquid aqueous coating or adhesive composition containing water as a continuous phase in an amount sufficient to achieve fluidity.

[0022] Here and throughout this specification, the terms “wt%” and “weight% (%bw)” are used synonymously.

[0023] Here, and throughout this specification, the term "pphm" means parts per 100 monomers, i.e., parts by weight per 100 parts monomer, and corresponds to a relative amount in weight percent of a particular substance based on the total amount of monomer M.

[0024] Here and throughout this specification, the term “ethylenically unsaturated monomer” is understood to mean that the monomer has at least one C=C double bond, e.g., 1, 2, 3, or 4 C=C double bonds, and these are radically polymerizable, i.e., polymerized under the conditions of an aqueous radical emulsion polymerization process to obtain a polymer having a carbon atom backbone. Here and throughout this specification, the term “monoethylenically unsaturated” is understood to mean that the monomer has a single C=C double bond and is readily subjected to radical polymerization under the conditions of aqueous radical emulsion polymerization.

[0025] Here and throughout this specification, the terms “ethoxylation” and “polyethoxylation” are used synonymously and refer to compounds having oligo- or polyoxyethylene groups formed by repeating units O-CH2CH2. In this context, the term “degree of ethoxylation” refers to the number average of the repeating units O-CH2CH2 in these compounds.

[0026] Here, and throughout this specification, the term “nonionic” in relation to compounds, in particular monomers, means that each compound does not have an ionic functional group or any functional group that can be converted to an ionic group by protonation or deprotonation.

[0027] Here and throughout this specification, the prefix C is used in relation to a compound or molecular part. n -C m Each of these indicates the range of possible numbers of carbon atoms that the molecular part or compound may have. n The term "alkyl" refers to a group of linear or branched saturated hydrocarbon radicals having 1 to n carbon atoms. n / C m The term "alkyl" refers to a mixture of two alkyl groups, one having n carbon atoms and the other having m carbon atoms.

[0028] For example, C1-C 20The term alkyl refers to a group of linear or branched saturated hydrocarbon radicals having 1 to 20 carbon atoms, the term C1-C4 alkyl refers to a group of linear or branched saturated hydrocarbon radicals having 1 to 4 carbon atoms, and C5-C 20 Alkyl represents a group of linear or branched saturated hydrocarbon radicals having 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 In the case of 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, henicosyldocosyl, and in the case of nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyldocosyl, their isomers, especially mixtures of isomers, such as "isononyl" and "isodecyl," but not limited to these. Examples of C1-C4 alkyl groups include, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, or 1,1-dimethylethyl.

[0029] The term "C5-C" used herein 20The term "-cycloalkyl" refers to a monocyclic, bicyclic, or tricyclic alicyclic radical that is unsubstituted or substituted with one, two, three, or four methyl radicals, and is C5-C 20 - The total number of carbon atoms in a cycloalkyl group is between 5 and 20. C5-C 20 -Examples of cycloalkyls include, but are not limited to, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclohexadecyl, norbornyl (=bicyclo[2.2.1]heptyl), and isobornyl (=1,7,7-trimethylbicyclo[2.2.1]heptyl). In cycloalkyls, one or two CH2 groups may be replaced by non-adjacent oxygen ring atoms to produce heteroalicyclic radicals. Examples of such radicals include, but are not limited to, oxolan-2-yl, oxolan-3-yl, oxan-2-yl, oxan-3-yl, oxan-4-yl, 1,3-dioxolan-2-yl, 1,3-dioxolan-4-yl, 2,2-dimethyl-1,3-dioxolan-4-yl, 1,4-dioxan-2-yl, 1,3-dioxan-2-yl, 1,3-dioxan-4-yl, 1,3-dioxan-5-yl, 2,2-dimethyl-1,3-dioxan-4-yl, and 2,2-dimethyl-1,3-dioxan-5-yl.

[0030] The term "C5-C" used herein 20 The term "-cycloalkylmethyl" refers to a C5-C5 group bonded via a methylene group, as defined herein. 20 - Refers to cycloalkyl radicals.

[0031] As used herein, the term "isobornyl" (=1,7,7-trimethylbicyclo[2.2.1]heptyl) refers to a monocyclic or alicyclic radical having 10 carbon atoms, which is either unsubstituted or substituted with 1, 2, 3, or 4 methyl radicals.

[0032] According to the present invention, monomer M comprises monomer M1, which is 1-heptyl acrylate.

[0033] 1-Heptyl acrylate is typically produced by esterification of acrylic acid with 1-heptanol, or by transesterification of methyl acrylate or ethyl acrylate with 1-heptanol. 1-Heptyl acrylate can be obtained from biological sources, at least with respect to its alkanol portion, and thus can enable the reduction of fossil carbon in polymer latex.

[0034] 1-Heptanol can be prepared from heptanal via catalytic hydrogenation, for example, as described in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag GmbH&Co.KGaA, Weinheim, 2012, vol.18, p.457 ff. Heptanal is preferably obtained, for example, by the thermal decomposition of ricinoleic acid or its esters, which are available from castor seed oil, i.e., a biomass source. The 1-heptanol thus prepared has a biocarbon content of about 100 mol%, and therefore makes it possible to produce 1-heptyl acrylate having a biocarbon content of at least 70 mol%.

[0035] The acrylic acid used for esterification can be obtained from fossil sources following standard procedures. Alternatively, acrylic acid can also be prepared from renewable raw materials, for example, according to International Publication No. 2006 / 092272, German Patent Application Publication No. 10 2006 039 203, or European Patent No. 2 922 580.

[0036] Preferably, at least a portion of the extract used to synthesize monomer M1 is derived from biorenewable raw materials. Therefore, specific embodiments of the present invention relate to polymer latexes as defined herein, in which at least the carbon atoms of the 1-heptyl groups in monomer M1 are of biological origin, i.e., they are made from at least partially biocarbon. In particular, the 1-heptanol used in the production of monomer M1 preferably has a biocarbon content of at least 90 mol%, based on the total amount of carbon atoms in the 1-heptanol. 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 and / or methacrylic acid produced from biomaterials have not been widely available to date. As a result, monomer M1 preferably has a biocarbon content of at least 63 mol%, particularly at least 69.5 mol%, based on the total amount of carbon atoms in the 1-heptyl acrylate. By using monomer M1 that is at least partially of biological origin, the demand for fossil carbon in polymer latexes can be significantly reduced. In particular, it is possible to achieve a bio-derived carbon content of at least 10 mol%, especially at least 15 mol%, or at least 20 mol%, for example, at least 30 mol%, or at least 40 mol%, at least 50 mol%, or at least 60 mol%.

[0037] The total amount of monomer M1 is 5 to 90% by weight, particularly 7.5 to 70% by weight, or 10 to 55% by weight, particularly 12 to 50% by weight, based on the total weight of monomer M.

[0038] In addition to monomer M1, the monomer M that forms the latex polymer may include one or more monomers M2 as defined above.

[0039] A suitable monomer M2 is: C2-C6 alkyl esters of acrylic acid, excluding tert-butyl acrylate, include but are not limited to ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, 2-methylbutyl acrylate, isoamyl acrylate (=3-methylbutyl acrylate), and 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 - C8-C acrylic acids, including but not limited to alkyl acrylates and stearyl acrylates. 20 -alkyl ester, 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 -Methacrylic acid C5-C, including but not limited to alkyl methacrylates and stearyl methacrylates. 20 -alkyl esters, and Those mixtures, It is selected from the group consisting of the following.

[0040] Preferred monomer M2 is selected from the group consisting of ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, 2-methylbutyl acrylate, isoamyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-octyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate, and mixtures thereof. Preferably, monomer M2 is selected from the group consisting of n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate and 2-octyl acrylate, and mixtures thereof. Isoamyl acrylate, 2-methylbutyl acrylate, isobutyl acrylate and / or 2-octyl acrylate may be produced from fossil sources or at least partially from bio-based sources. In particular, the carbon atoms of the isoamyl, 2-methylbutyl, isobutyl, and / or 2-octyl groups of isoamyl acrylate, 2-methylbutyl acrylate, isobutyl acrylate, and 2-octyl acrylate, respectively, are of biological origin; that is, the monomers are obtained by esterifying acrylic acid, which may be of bio-derived or fossil-derived origin, with bio-derived isoamyl alcohol, 2-methylbutanol, isobutanol, or 2-octanol, respectively. In particular, the isobutyl group of isobutyl acrylate and / or the 2-octanol group of 2-octyl acrylate are of biological origin; that is, the monomers are obtained by esterifying acrylic acid, which may be of bio-derived or fossil-derived origin, with bio-derived isobutanol or 2-octanol, respectively.

[0041] In the preferred group M2-A of the embodiments, monomer M2 includes isobutyl acrylate, particularly bio-based isobutyl acrylate. In particular, monomer M2 is isobutyl acrylate, particularly bio-based isobutyl acrylate. In this preferred group of embodiments, monomer M2 also includes isobutyl acrylate and at least one further C2-C6 or C8-C different from isobutyl acrylate. 10Alkyl acrylates, for example, particularly n-butyl acrylate, isoamyl acrylate, 2-methylbutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate, or mixtures thereof, particularly n-butyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate.

[0042] In relation to this group of embodiments, the amount of isobutyl acrylate is preferably in the range of 1 to 70% by weight, particularly 10 to 60% by weight, and particularly 20 to 50% by weight, based on the total amount of monomer M.

[0043] In another preferred group M2-B of the embodiments, monomer M2 comprises, and more particularly, n-butyl acrylate. In this group of embodiments, n-butyl acrylate may be the sole monomer, or n-butyl acrylate and at least one further C2-C6 or C8-C different from n-butyl acrylate. 10 Alkyl acrylates, for example, particularly isobutyl acrylate, isoamyl acrylate, 2-methylbutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate, or mixtures thereof, particularly isobutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate.

[0044] In relation to this group of embodiments, the amount of n-butyl acrylate is preferably in the range of 1 to 60% by weight, particularly 10 to 50% by weight, and particularly 15 to 40% by weight, based on the total amount of monomer M.

[0045] Isobutyl acrylate, 2-methylbutyl acrylate, isopentyl acrylate, and 2-octyl acrylate are typically produced by esterification of acrylic acid with isobutanol (2-methylpropane-1-ol), 2-methylbutanol, isopentanol (3-methylbutan-1-ol), or 2-octanol, or by transesterification of methyl acrylate or ethyl acrylate with isobutanol (2-methylpropane-1-ol), 2-methylbutan-1-ol, isopentanol (3-methylbutan-1-ol), or 2-octanol, respectively.

[0046] 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, and thus from biological or renewable feedstocks, respectively. In particular, fermentation can produce mixtures containing different alkanols, such as isobutanol, 2-methylbutan-1-ol, and 3-methylbutan-1-ol, which can be separated by conventional techniques, e.g., fractional distillation. This can yield pure alcohols (over 90% purity) or mixtures containing at least 80%, particularly at least 90%, in total amount of at least two alcohols selected from the group consisting of isobutanol, 2-methylbutan-1-ol, and 3-methylbutan-1-ol. For example, a mixture containing at least 80% by weight of a mixture 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 within the range of 1:1 to 10:1. 2-Octanol can be produced by alkali-catalyzed thermal cleavage of ricinoleic acid with sebacic acid as a byproduct. Castor oil, mainly composed of ricinoleic acid, is the primary source material. Therefore, the inclusion of these monomers M2 in 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 polymer latex.

[0047] Accordingly, specific embodiments of the present invention relate to polymer latexes as defined herein in which at least the carbon atoms of the isobutyl group, 2-methylbutyl group, isoamyl group, and 2-octyl group in monomer M2, and in particular the carbon atoms of the isobutyl group in monomer M2, are of biological origin, i.e., are made at least partially from biocarbon. In particular, isobutanol, 2-methylbutan-1-ol, 3-methylbutanol, and 2-octanol used in the production of monomer M2 preferably have a biocarbon content of at least 90 mol% based on the total amount of carbon atoms in isobutanol, 2-methylpentanol, 3-methylbutanol, and 2-octanol. 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 made available on a large scale to date. As a result, monomer M2 preferably has a biocarbon content of at least 51 mol%, particularly at least 54 mol%, and particularly 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 monomer M2 which is at least partially of biological origin, the demand for fossil carbon in polymer latex can be significantly reduced. In particular, it is possible to achieve an amount of bio-derived carbon of at least 5 mol%, particularly at least 10 mol%, or at least 15 mol%, for example, 20 mol%, or 30 mol%, or more.

[0048] The total amount of monomer M2 is 0 to 70% by weight, particularly 0 to 60% by weight or 1 to 60% by weight, particularly 1 to 50% by weight or 5 to 50% by weight, based on the total weight of monomer M.

[0049] In a specific group M2-1 of the embodiments, monomer M is determined based on the total amount of monomer M. A monomer M1 in an amount of 15 to 80% by weight, preferably 20 to 70% by weight, and particularly 25 to 60% by weight, A monomer M2 in an amount of 0 to less than 5% by weight, preferably 0 to 3% by weight, and especially 0% by weight, Based on the total amount of monomer M, monomer M3 contains or is composed of methyl methacrylate in an amount of 20 to 70% by weight, preferably 30 to 70% by weight, and particularly 40 to 65% by weight. Includes.

[0050] In a further specific group M2-2 of the embodiments, monomer M is based on the total amount of monomer M, A monomer M1 in an amount of 5 to 50% by weight, preferably 5 to 30% by weight, and especially 5 to 20% by weight, 5 to 70% by weight, preferably 15 to 60% by weight, particularly 20 to 50% by weight, monomer M2 as defined according to the above group M2-A of embodiments, i.e., monomer M2 is selected from isobutyl acrylate in particular, as well as mixtures of isobutyl acrylate and at least one of n-butyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate, wherein the carbon atoms of isobutyl acrylate and, if present, 2-octyl acrylate are preferably at least partially of biological origin, monomer M2 and A monomer M3 containing or being methyl methacrylate in an amount of 10 to 70% by weight, preferably 20 to 65% by weight, and particularly 30 to 62% by weight, Includes.

[0051] In further specific groups M2-3 of the embodiments, monomer M is based on the total amount of monomer M. A monomer M1 in an amount of 5 to 50% by weight, preferably 5 to 30% by weight, and especially 5 to 20% by weight, A monomer M2 defined according to the above-described group M2-B of embodiments, in an amount of 5 to 70% by weight, preferably 15 to 60% by weight, and particularly 20 to 50% by weight, wherein the monomer M2 is selected from n-butyl acrylate in particular, as well as mixtures of n-butyl acrylate with at least one of isobutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate, and, if present, the carbon atoms of isobutyl acrylate and 2-octyl acrylate are preferably at least partially of biological origin, and the monomer M2 is, A monomer M3 containing or being methyl methacrylate in an amount of 10 to 70% by weight, preferably 20 to 65% by weight, and particularly 30 to 62% by weight, Includes.

[0052] Here, the groups M2-1 and M2-2 of the embodiments, and particularly the group M2-2 of the embodiments, are especially preferred.

[0053] In addition to monomers M1 and M2, the monomer M that forms the latex polymer may include one or more monomers M3 as defined above.

[0054] A suitable monomer M3 is: C1-C4 alkyl esters of methacrylic acid, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate. tert-butyl acrylate, C5-C (meth)acrylic acids, including but not limited to cyclopentyl acrylate, cyclopentyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, norbornyl acrylate, norbornyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 1,3-dioxan-5-yl acrylate, 1,3-dioxan-5-yl methacrylate, 2,2-dimethyl-1,3-dioxan-5-yl acrylate, and 2,2-dimethyl-1,3-dioxan-5-yl methacrylate. 20 -Cycloalkyl ester, C5-C (meth)acrylic acids, including but not limited to cyclopentyl methyl acrylate, cyclopentyl methyl methacrylate, cyclohexyl methyl acrylate, cyclohexyl methyl methacrylate, 1,3-dioxolan-4-yl methyl acrylate, 1,3-dioxolan-4-yl methyl methacrylate, 2,2-dimethyl-1,3-dioxolan-4-yl methyl acrylate, 2,2-dimethyl-1,3-dioxolan-4-yl methyl methacrylate, oxolan-2-yl methyl acrylate (tetrahydrofurfuryl acrylate), and oxolan-2-yl methyl methacrylate (tetrahydrofurfuryl methacrylate). 20 -Cycloalkylmethyl ester, Methylene-gamma-butyrolactone, for example, alpha-methylene-gamma-butyrolactone or gamma-methylene-gamma-butyrolactone, Monovinyl aromatic monomers, for example, styrene, 2-methylstyrene or 4-methylstyrene, and Those mixtures, It is selected from the group consisting of the following.

[0055] In the preferred group of embodiments, monomer M3 is C1-C4 alkyl esters of methacrylic acid, especially methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and tert-butyl methacrylate, tert-butyl acrylate, Cyclopentyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, Alpha-methylene-gamma-butyrolactone, Styrene, and Those mixtures, It is selected from the group consisting of the following.

[0056] In this group, monomer M3 is particularly, Methyl methacrylate, n-butyl methacrylate, tert-butyl acrylate, Cyclopentyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, Alpha-methylene-gamma-butyrolactone, Styrene, and Those mixtures, It is selected from the group consisting of the following.

[0057] In a particular group of embodiments, monomer M3 comprises at least 50% by weight, particularly at least 80% or 100% by weight, of methyl methacrylate based on the total amount of monomer M3 in monomer M. More specifically in this group, monomer M3 is selected from the group consisting of combinations of methyl methacrylate and methyl methacrylate with at least one further monomer M3 selected from n-butyl methacrylate, tert-butyl acrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, alpha-methylene-gamma-butyrolactone, and styrene, particularly at least one further monomer M3 selected from n-butyl methacrylate, tert-butyl acrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, and styrene.

[0058] In this particular group of embodiments, monomer M3, which is methyl methacrylate, is preferred.

[0059] The total amount of monomer M3 is 5 to 70% by weight, particularly 15 to 70% by weight, or 25 to 65% by weight, particularly 35 to 62% by weight, based on the total weight of monomer M.

[0060] The total amount of monomers M1 and M2 is preferably in the range of 10 to 90% by weight, particularly in the range of 20 to 80% by weight, and especially in the range of 25 to 70% by weight, based on the total amount of ethylenically unsaturated monomer M.

[0061] The total amount of monomers M1, M2, and M3 is at least 90% by weight, particularly at least 94% by weight, and particularly at least 97% by weight, based on the total amount of ethylenically unsaturated monomer M.

[0062] The weight ratio of M1 to M3 is generally in the range of 1:10 to 5:1, particularly in the range of 1:6 to 3:1, preferably in the range of 1:5 to 2:1, and especially in the range of 1:4 to 1.5:1.

[0063] When M2 is present, the weight ratio of M1 to M2 is generally in the range of 1:10 to 2:1, particularly in the range of 1:4 to 1.5:1, and preferably in the range of 1:3 to 1:1.

[0064] Monomer M may further comprise at least one monomer M4 selected from monoethylenically unsaturated monomers having an acidic group.

[0065] Suitable monomers M4 include: Monoethylenically unsaturated monocarboxylic acids having 3 to 6 carbon atoms, for example, 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, for example, itaconic acid, citraconic acid, and fumaric acid. A semi-ester of a monoethylenically unsaturated dicarboxylic acid having 4 to 6 carbon atoms with a C1-C4 alkanol, for example, methanol or ethanol, for example, itaconic acid, citraconic acid, maleic acid or fumaric acid with methanol or ethanol. Monoethylenically unsaturated sulfonic acids, for example, vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, Monoethylenically unsaturated phosphonic acids, such as vinylphosphonic acid, allylphosphonic acid, styrenephosphonic acid, and 2-acrylamido-2-methylpropanephosphonic acid. Monoethylene unsaturated phosphoric acid, for example, monophosphates of hydroxyalkyl acrylates, monophosphates of hydroxyalkyl methacrylates, monophosphates of alkoxylylated hydroxyalkyl acrylates and monophosphates of alkoxylylated hydroxyalkyl methacrylates, particularly 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 methacrylate and monophosphates of propoxylated hydroxy-C2-C4-alkyl methacrylate. These include, but are not limited to, the following:

[0066] The aforementioned monomers M4 can exist in their acidic forms or in the form of their salts, particularly in the form of their alkali metal salts or ammonium salts.

[0067] Among the monomers M4 described above, 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, and combinations thereof are particularly preferred. Monoethylenically unsaturated monocarboxylic acids and monoethylenically unsaturated dicarboxylic acids, and their salts, particularly alkali metal salts and ammonium salts, particularly acrylic acid, methacrylic acid, itaconic acid, and their salts, particularly alkali metal salts and ammonium salts, and combinations thereof are more preferred. In certain groups of embodiments, monomer M4 includes acrylic acid or its salts, particularly alkali metal salts or ammonium salts. In particular, monomer M4 is acrylic acid or its salts, particularly alkali metal salts or ammonium salts, or a mixture of acrylic acid and methacrylic acid or its salts, particularly alkali metal salts or ammonium salts. In another specific group of embodiments, monomer M4 includes methacrylic acid or a salt thereof, particularly an alkali metal salt or an ammonium salt. In particular, monomer M4 is methacrylic acid or a salt thereof, particularly an alkali metal salt or an ammonium salt.

[0068] The total amount of monomer M4 is 0.05 to 5% by weight or 0.1 to 4% by weight, particularly 0.05 to 3.5% by weight or 0.1 to 3% by weight, particularly 0.2 to 2.5% by weight or 0.5 to 2% by weight or 0.5 to 1.5% by weight, based on the total weight of monomer M.

[0069] The monomer M may further contain at least one monoethylenically unsaturated nonionic monomer M5 having a solubility of at least 60 g / L in deionized water at 20°C and 1 bar.

[0070] Preferred monomers M5 are selected from the group consisting of nonionic monoethylenically unsaturated monomers having a functional group selected from the group consisting of hydroxyalkyl groups, particularly hydroxy-C2-C4-alkyl groups, primary carboxamide groups, urea groups, keto groups, and combinations thereof.

[0071] The total amount of monomer M5 does not usually exceed 10% by weight, and especially 7% by weight, based on the total amount of monomer M. In particular, the total amount of monomer M5 is usually 0 to 9.95% by weight, and if present, 0.05 to 9.95% by weight, especially 0.1 to 7% by weight, especially 0.1 to 5% by weight or 0.1 to 4% by weight or 0.5 to 3% by weight or 1 to 3% by weight, based on the total weight of monomer M.

[0072] Examples of monomer M5 (hereinafter referred to as monomer M5a) having a carboxamide group 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 acrylamide and methacrylamide, and in particular arylamide.

[0073] Examples of monomer M5 (hereinafter referred to as monomer M5b) having a urea group are C1-C4-alkyl esters of acrylic acid or methacrylic acid and N-C1-C4-alkylamides of acrylic acid or methacrylic acid, where the C1-C4-alkyl group is either a urea group or a 2-oxoimidazolin group, for example, 2-(2-oxo-imidazolidin-1-yl)ethyl acrylate, 2-(2-oxo-imidazolidin-1-yl)ethyl methacrylate (2-ureidoacrylate and 2-ureidoacrylate, respectively). These include N-(2-acryloxyethyl)urea, N-(2-methacryloxyethyl)urea, N-(2-(2-oxo-imidazolidined-1-yl)ethyl)acrylamide, N-(2-(2-oxo-imidazolidined-1-yl)ethyl)methacrylamide, as well as allyl or vinyl-substituted ureas and allyl or vinyl-substituted 2-oxoimidazolin compounds, such as 1-allyl-2-oxoimidazolin, N-allylurea, and N-vinylurea.

[0074] Examples of monomers M5 (hereinafter referred to as monomer M5c) that have a keto group are: C2-C8-oxoalkyl esters of acrylic acid or methacrylic acid and N-C2-C8-oxoalkylamides of acrylic acid or methacrylic acid, for example, diacetoneacrylamide (DAAM) and diacetonemethacrylamide, and These are C1-C4-alkyl esters of acrylic acid or methacrylic acid and N-C1-C4-alkylamides of acrylic acid or methacrylic acid, wherein the C1-C4-alkyl group is a 2-acetylacetoxy group of the formula OC(=O)-CH2-C(=O)-CH3 (also called an acetacetoxy group), such as acetoxyethyl acrylate, acetoxypropyl methacrylate, acetacetoxybutyl methacrylate, and 2-(acetacetoxy)ethyl methacrylate.

[0075] In certain groups of embodiments, monomer M5 includes acrylamide or methacrylamide, and more particularly includes acrylamide. In particular, monomer M4 is acrylamide or methacrylamide, and more particularly acrylamide.

[0076] Preferably, monomer M is i. Based on the total amount of monomer M, 5 to 90% by weight, particularly 7.5 to 70% by weight or 10 to 55% by weight, particularly 12 to 50% by weight, 1-heptyl acrylate as monomer M1, ii. Based on the total amount of monomer M, at least one monomer M2 comprising or being isobutyl acrylate in an amount of 0 to 70% by weight, particularly 0 to 60% by weight or 1 to 60% by weight, particularly 1 to 50% by weight or 5 to 50% by weight, iii. Based on the total amount of monomer M, at least one monomer M3 containing or being methyl methacrylate in an amount of 5 to 70% by weight, particularly 15 to 70% by weight or 25 to 65% by weight, particularly 35 to 62% by weight, iv. Based on the total amount of monomer M, one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having acidic groups, in an amount of 0.05 to 5% by weight or 0.1 to 4% by weight, particularly 0.05 to 3.5% by weight or 0.1 to 3% by weight, particularly 0.2 to 3% by weight or 0.5 to 3% by weight or 0.5 to 2% by weight, v. If present, one or more nonionic monomers M5 having solubility in deionized water at 20°C and 1 bar of at least 60 g / L, based on the total weight of monomer M, in amounts of 0 to 9.95% by weight, 0.05 to 9.95% by weight, particularly 0.1 to 7% by weight, particularly 0.1 to 5% by weight, or 0.1 to 4% by weight, or 0.5 to 3% by weight, or 1 to 3% by weight, or, i. Based on the total amount of monomer M, 5 to 90% by weight, particularly 7.5 to 70% by weight or 10 to 55% by weight, particularly 12 to 50% by weight, 1-heptyl acrylate as monomer M1, ii. Based on the total amount of monomer M, at least one monomer M2 containing or being n-butyl acrylate in an amount of 0 to 70% by weight, particularly 0 to 60% by weight or 1 to 60% by weight, particularly 1 to 50% by weight or 5 to 50% by weight, iii. Based on the total amount of monomer M, at least one monomer M3 containing or being methyl methacrylate in an amount of 5 to 70% by weight, particularly 15 to 70% by weight or 25 to 65% by weight, particularly 35 to 62% by weight, iv. Based on the total amount of monomer M, one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having acidic groups, in an amount of 0.05 to 5% by weight or 0.1 to 4% by weight, particularly 0.05 to 3.5% by weight or 0.1 to 3% by weight, particularly 0.2 to 3% by weight or 0.5 to 3% by weight or 0.5 to 2% by weight, v. If present, one or more nonionic monomers M5 having solubility in deionized water at 20°C and 1 bar of at least 60 g / L, based on the total weight of monomer M, in amounts of 0 to 9.95% by weight, 0.05 to 9.95% by weight, particularly 0.1 to 7% by weight, particularly 0.1 to 5% by weight, or 0.1 to 4% by weight, or 0.5 to 3% by weight, or 1 to 3% by weight, The material contains or consists of the following, the total amount of monomers M1 and M3 is in the range of 10 to 98% by weight, particularly 22.5 to 85% by weight, particularly 35 to 70% by weight, based on the total amount of ethylenically unsaturated monomer M, and the total amount of monomers M1, M2 and M3 is at least 90% by weight, particularly at least 94% by weight, particularly at least 97% by weight, based on the total amount of ethylenically unsaturated monomer M.

[0077] In a specific group 1 of the embodiments, monomer M is i. Based on the total amount of monomer M, 1-heptyl acrylate as monomer M1 is present in an amount of 15 to 79.95% by weight, particularly 20 to 69.85% by weight, particularly 25 to 59.4% by weight, ii. Based on the total amount of monomer M, monomer M3 contains or is composed of methyl methacrylate in an amount of 20 to 70% by weight, particularly 30 to 70% by weight, particularly 40 to 65% by weight, iii. Based on the total amount of monomer M, one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having acidic groups, in an amount of 0.05 to 5% by weight, particularly 0.1 to 4% by weight, particularly 0.5 to 3% by weight, iv. Based on the total weight of monomer M, one or more nonionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20°C and 1 bar, in amounts of 0 to 9.95% by weight, particularly 0.05 to 5% by weight, and particularly 0.1 to 4% by weight, It contains or consists of the following, and the total amount of monomers M1 and M3 is at least 85% by weight, particularly at least 90% by weight, particularly at least 95% by weight, based on the total amount of ethylenically unsaturated monomer M. or, i. Based on the total amount of monomer M, 5 to 50% by weight, especially 5 to 30% by weight, especially 5 to 20% by weight, of 1-heptyl acrylate as monomer M1, ii. Based on the total amount of monomer M, isobutyl acrylate as monomer M2 in an amount of 5 to 70% by weight, particularly 15 to 60% by weight, particularly 20 to 50% by weight, iii. Based on the total amount of monomer M, monomer M3 contains or is composed of methyl methacrylate in an amount of 10 to 70% by weight, particularly 20 to 65% by weight, particularly 30 to 62% by weight, iv. Based on the total amount of monomer M, one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having acidic groups, in an amount of 0.05 to 5% by weight, particularly 0.1 to 4% by weight, and particularly 0.5 to 3% by weight, v. Based on the total weight of monomer M, one or more nonionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20°C and 1 bar, in amounts ranging from 0 to 9.95% by weight, particularly 0.05 to 5% by weight, and particularly 0.1 to 4% by weight, The material contains or consists of the following, the total amount of monomers M1 and M3 is in the range of 15 to 90% by weight, particularly 25 to 80% by weight, particularly 35 to 70% by weight, based on the total amount of ethylenically unsaturated monomer M, and the total amount of monomers M1, M2 and M3 is at least 90% by weight, particularly at least 94% by weight, particularly at least 97% by weight, based on the total amount of ethylenically unsaturated monomer M. or, i. Based on the total amount of monomer M, 5 to 50% by weight, especially 5 to 30% by weight, especially 5 to 20% by weight, of 1-heptyl acrylate as monomer M1, ii. Based on the total amount of monomer M, monomer M2 is a mixture of isobutyl acrylate and at least one of n-butyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate in an amount of 5 to 70% by weight, particularly 15 to 60% by weight, particularly 20 to 50% by weight, iii. Based on the total amount of monomer M, monomer M3 contains or is composed of methyl methacrylate in an amount of 10 to 70% by weight, particularly 20 to 65% by weight, particularly 30 to 62% by weight, iv. Based on the total amount of monomer M, one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having acidic groups, in an amount of 0.05 to 5% by weight, particularly 0.1 to 4% by weight, and particularly 0.5 to 3% by weight, v. Based on the total weight of monomer M, one or more nonionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20°C and 1 bar, in amounts ranging from 0 to 9.95% by weight, particularly 0.05 to 5% by weight, and particularly 0.1 to 4% by weight, The material contains or consists of the following, the total amount of monomers M1 and M3 is in the range of 15 to 90% by weight, particularly 25 to 80% by weight, particularly 35 to 70% by weight, based on the total amount of ethylenically unsaturated monomer M, and the total amount of monomers M1, M2 and M3 is at least 90% by weight, particularly at least 94% by weight, particularly at least 97% by weight, based on the total amount of ethylenically unsaturated monomer M. or, i. Based on the total amount of monomer M, 5 to 50% by weight, especially 5 to 30% by weight, especially 5 to 20% by weight, of 1-heptyl acrylate as monomer M1, ii. Based on the total amount of monomer M, monomer M2 is provided in an amount of 5 to 70% by weight, particularly 15 to 60% by weight, particularly 20 to 50% by weight, which is selected from n-butyl acrylate and combinations of n-butyl acrylate with at least one of isobutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate. iii. Based on the total amount of monomer M, monomer M3 contains or is composed of methyl methacrylate in an amount of 10 to 70% by weight, particularly 20 to 65% by weight, particularly 30 to 62% by weight, iv. Based on the total amount of monomer M, one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having acidic groups, in an amount of 0.05 to 5% by weight, particularly 0.1 to 4% by weight, and particularly 0.5 to 3% by weight, v. Based on the total weight of monomer M, one or more nonionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20°C and 1 bar, in amounts ranging from 0 to 9.95% by weight, particularly 0.05 to 5% by weight, and particularly 0.1 to 4% by weight, The total amount of monomers M1 and M3 is in the range of 15 to 90% by weight, particularly 25 to 80% by weight, particularly 35 to 70% by weight, based on the total amount of ethylenically unsaturated monomer M, and the total amount of monomers M1, M2 and M3 is at least 90% by weight, particularly at least 94% by weight, particularly at least 97% by weight, based on the total amount of ethylenically unsaturated monomer M.

[0078] In a specific subgroup 1a of group 1 of the embodiments, monomer M is i. Based on the total amount of monomer M, 15 to 79.95% by weight, particularly 20 to 69.85% by weight, particularly 25 to 59.4% by weight, of 1-heptyl acrylate as monomer M1, wherein at least the carbon atoms of the 1-heptyl group in the 1-heptyl acrylate are of biological origin, and particularly the biocarbon content of the 1-heptyl acrylate is at least 63 mol%, particularly at least 69.5 mol%, and 1-heptyl acrylate, ii. Based on the total amount of monomer M, monomer M3 contains or is composed of methyl methacrylate in an amount of 20 to 70% by weight, particularly 30 to 70% by weight, particularly 40 to 65% by weight, iii. Based on the total amount of monomer M, one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having acidic groups, in an amount of 0.05 to 5% by weight, particularly 0.1 to 4% by weight, particularly 0.5 to 3% by weight, iv. Based on the total weight of monomer M, one or more nonionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20°C and 1 bar, in amounts of 0 to 9.95% by weight, particularly 0.05 to 5% by weight, and particularly 0.1 to 4% by weight, It contains or consists of the following, and the total amount of monomers M1 and M3 is at least 85% by weight, particularly at least 90% by weight, particularly at least 95% by weight, based on the total amount of ethylenically unsaturated monomer M. or, i. Based on the total amount of monomer M, 5 to 50% by weight, particularly 5 to 30% by weight, particularly 5 to 20% by weight, of 1-heptyl acrylate as monomer M1, wherein at least the carbon atoms of the 1-heptyl group in the 1-heptyl acrylate are of biological origin, and particularly the biocarbon content of the 1-heptyl acrylate is at least 63 mol%, particularly at least 69.5 mol%, and ii. Based on the total amount of monomer M, isobutyl acrylate as monomer M2 in an amount of 5 to 70% by weight, particularly 15 to 60% by weight, particularly 20 to 50% by weight, wherein at least the carbon atoms of the isobutyl group in the isobutyl acrylate are of biological origin, and the biocarbon content of the isobutyl acrylate is at least 54 mol%, particularly at least 57 mol%, and iii. Based on the total amount of monomer M, monomer M3 contains or is composed of methyl methacrylate in an amount of 10 to 70% by weight, particularly 20 to 65% by weight, particularly 30 to 62% by weight, iv. Based on the total amount of monomer M, one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having acidic groups, in an amount of 0.05 to 5% by weight, particularly 0.1 to 4% by weight, and particularly 0.5 to 3% by weight, v. Based on the total weight of monomer M, one or more nonionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20°C and 1 bar, in amounts ranging from 0 to 9.95% by weight, particularly 0.05 to 5% by weight, and particularly 0.1 to 4% by weight, The material contains or consists of the following, the total amount of monomers M1 and M3 is in the range of 15 to 90% by weight, particularly 25 to 80% by weight, particularly 35 to 70% by weight, based on the total amount of ethylenically unsaturated monomer M, and the total amount of monomers M1, M2 and M3 is at least 90% by weight, particularly at least 94% by weight, particularly at least 97% by weight, based on the total amount of ethylenically unsaturated monomer M. or, i. Based on the total amount of monomer M, 5 to 50% by weight, particularly 5 to 30% by weight, particularly 5 to 20% by weight, of 1-heptyl acrylate as monomer M1, wherein at least the carbon atoms of the 1-heptyl group in the 1-heptyl acrylate are of biological origin, and particularly the biocarbon content of the 1-heptyl acrylate is at least 63 mol%, particularly at least 69.5 mol%, and ii. Monomer M2 is a mixture of isobutyl acrylate and at least one of n-butyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate in an amount of 5 to 70% by weight, particularly 15 to 60% by weight, particularly 20 to 50% by weight, based on the total amount of monomer M, wherein at least the carbon atoms of the isobutyl group in the isobutyl acrylate are of biological origin, and the biocarbon content of the isobutyl acrylate is at least 54 mol%, particularly at least 57 mol%, and monomer M2, iii. Based on the total amount of monomer M, monomer M3 contains or is composed of methyl methacrylate in an amount of 10 to 70% by weight, particularly 20 to 65% by weight, particularly 30 to 62% by weight, iv. Based on the total amount of monomer M, one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having acidic groups, in an amount of 0.05 to 5% by weight, particularly 0.1 to 4% by weight, and particularly 0.5 to 3% by weight, v. Based on the total weight of monomer M, one or more nonionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20°C and 1 bar, in amounts ranging from 0 to 9.95% by weight, particularly 0.05 to 5% by weight, and particularly 0.1 to 4% by weight, The material contains or consists of the following, the total amount of monomers M1 and M3 is in the range of 15 to 90% by weight, particularly 25 to 80% by weight, particularly 35 to 70% by weight, based on the total amount of ethylenically unsaturated monomer M, and the total amount of monomers M1, M2 and M3 is at least 90% by weight, particularly at least 94% by weight, particularly at least 97% by weight, based on the total amount of ethylenically unsaturated monomer M. or, i. Based on the total amount of monomer M, 5 to 50% by weight, particularly 5 to 30% by weight, particularly 5 to 20% by weight, of 1-heptyl acrylate as monomer M1, wherein at least the carbon atoms of the 1-heptyl group in the 1-heptyl acrylate are of biological origin, and particularly the biocarbon content of the 1-heptyl acrylate is at least 63 mol%, particularly at least 69.5 mol%, and ii. Based on the total amount of monomer M, monomer M2 is provided in an amount of 5 to 70% by weight, particularly 15 to 60% by weight, particularly 20 to 50% by weight, which is selected from n-butyl acrylate and combinations of n-butyl acrylate with at least one of isobutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate. iii. Based on the total amount of monomer M, monomer M3 contains or is composed of methyl methacrylate in an amount of 10 to 70% by weight, particularly 20 to 65% by weight, particularly 30 to 62% by weight, iv. Based on the total amount of monomer M, one or more monoethylenically unsaturated monomers M4 selected from monoethylenically unsaturated monomers having acidic groups, in an amount of 0.05 to 5% by weight, particularly 0.1 to 4% by weight, and particularly 0.5 to 3% by weight, v. Based on the total weight of monomer M, one or more nonionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20°C and 1 bar, in amounts ranging from 0 to 9.95% by weight, particularly 0.05 to 5% by weight, and particularly 0.1 to 4% by weight, The total amount of monomers M1 and M3 is in the range of 15 to 90% by weight, particularly 25 to 80% by weight, particularly 35 to 70% by weight, based on the total amount of ethylenically unsaturated monomer M, and the total amount of monomers M1, M2 and M3 is at least 90% by weight, particularly at least 94% by weight, particularly at least 97% by weight, based on the total amount of ethylenically unsaturated monomer M.

[0079] In addition to the monomers M1, M2, M3, M4, and M5 described above, monomer M may include one or more further monomers different from monomer M described above. Suitable monomers M different from monomers M1, M2, M3, M4, and M5 include: Monomer M6 selected from monoethylenically unsaturated nonionic monomers having a silane functional group or an epoxy group, Monomer M7 is selected from multi-ethylenically unsaturated monomers, i.e., monomers having at least two non-conjugated ethylenically unsaturated double bonds. Monomer M8 selected from monoethylene unsaturated copolymerizable UV initiators, These include, but are not limited to, the following:

[0080] Suitable monomers M6 include monoethylenically unsaturated silane-functional monomers (monomer M6a), such as monomers having at least one mono-, di-, and / or tri-C1-C4-alkoxysilane group in addition to an ethylenically unsaturated double bond, such as vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxyethyltrimethoxysilane, methacryloxyethyltriethoxysilane, and mixtures thereof. Methacryloxypropyltrimethoxysilane and vinyltriethoxysilane are preferred. The amount of silane-functional monomer M6a, if present, is usually not 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, based on the total amount of ethylenically unsaturated monomer M.

[0081] Suitable monomers M6 also include monoethylenically unsaturated monomers (monomer M6b) having at least one epoxy group, particularly a glycidyl group, such as glycidyl acrylate, glycidyl methacrylate, 2-glycidyloxyethyl acrylate, and 2-glycidyloxyethyl methacrylate. The amount of monomer M6b, if present, is usually not more than 2% by weight, often in the range of 0.01 to 2% by weight, preferably in the range of 0.05 to 1% by weight, based on the total amount of ethylenically unsaturated monomer M.

[0082] Monomer M may also include a multi-ethylenically unsaturated monomer (monomer M7), i.e., a monomer having at least two non-conjugated ethylenically unsaturated double bonds. The amount of monomer M7 is generally not more than 1% by weight, often in the range of 0 to 1% by weight, and particularly 0 to 0.5% by weight, based on the total amount of ethylenically unsaturated monomer M.

[0083] Examples of multi-ethylene unsaturated monomers M7 include: Diesters of monoethylenically unsaturated C3-C6 monocarboxylic acids with saturated aliphatic or alicyclic diols, particularly diesters of acrylic acid or methacrylic acid, such as 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, diacrylates and dimethacrylates. Monoesters of monoethylenically unsaturated C3-C6 monocarboxylic acids and monoethylenically unsaturated aliphatic or alicyclic monohydroxy compounds, for example, acrylates and methacrylates of vinyl alcohol (ethenol), allyl alcohol (2-propen-1-ol), 2-cyclohexen-1-ol, or norborneol, for example, allyl acrylate and allyl methacrylate, and Divinyl aromatic compounds, for example, 1,3-divinylbenzene, 1,4-divinylbenzene, These are some examples.

[0084] The polymerized monoethylenically unsaturated copolymerizable UV initiator M8 results in crosslinking of polymer chains upon exposure to sunlight. Monomer M8 has ethylenically unsaturated double bonds, particularly acrylate or methacrylate groups, and moieties that decompose upon UV irradiation, thereby forming radicals. Such groups are typically benzophenone, acetophenone, benzoin, or carbonate groups bonded to a phenyl ring. Such compounds are disclosed, for example, in European Patent No. 346734, European Patent No. 377199, German Patent No. 4037079, German Patent No. 3844444, European Patent No. 1213, and U.S. Patent Application Publication 2015 / 0152297. Examples include, but are not limited to, 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-methylpropenoate), O-(2-(meth)acryloxyethyl)-O-(benzoylphenyl)carbonate, and O-(2-(meth)acryloxyethyl)-O-(acetylphenyl)carbonate. The amount of monomer M8 generally does not exceed 1% by weight, and when present, is typically in the range of 0.01 to 1% by weight, particularly 0.02 to 0.5% by weight, based on the total amount of ethylenically unsaturated monomer M.

[0085] In a specific group 2 of the embodiment, monomer M is i. Based on the total amount of monomer M, 15 to 79.95% by weight, particularly 20 to 69.85% by weight, particularly 25 to 59.4% by weight, of 1-heptyl acrylate as monomer M1, wherein at least the carbon atoms of the 1-heptyl group in the 1-heptyl acrylate are of biological origin, and particularly the biocarbon content of the 1-heptyl acrylate is at least 63 mol%, particularly at least 69.5 mol%, and 1-heptyl acrylate, ii. Based on the total amount of monomer M, monomer M3 contains or is composed of methyl methacrylate in an amount of 20 to 70% by weight, particularly 30 to 70% by weight, particularly 40 to 65% by weight, iii. Based on the total amount of monomer M, one or more monoethylenically unsaturated monomers M4 selected from acrylic acid, methacrylic acid, itaconic acid and combinations thereof, in an amount of 0.05 to 5% by weight, particularly 0.1 to 4% by weight, particularly 0.5 to 3% by weight, iv. One or more nonionic monomers M5 having a solubility of at least 60 g / L in deionized water at 20°C and 1 bar, in an amount of 0 to 9.95% by weight, particularly 0.05 to 5% by weight, particularly 0.1 to 4% by weight, and having a functional group selected from the group consisting of hydroxyalkyl groups, primary carboxamide groups, urea groups, keto groups, and combinations thereof, nonionic monomers M5, v. Based on the total weight of monomer M, one or more monomers M7 in an amount of 0 to 1% by weight, particularly 0 to 0.5% by weight, It consists of the following, and the total amount of monomers M1 and M3 is at least 85% by weight, particularly at least 90% by weight, particularly at least 95% by weight, based on the total amount of ethylenically unsaturated monomer M. or, i. Based on the total amount of monomer M, 5 to 50% by weight, particularly 5 to 30% by weight, particularly 5 to 20% by weight, of 1-heptyl acrylate as monomer M1, wherein at least the carbon atoms of the 1-heptyl group in the 1-heptyl acrylate are of biological origin, and particularly the biocarbon content of the 1-heptyl acrylate is at least 63 mol%, particularly at least 69.5 mol%, and ii. Based on the total amount of monomer M, isobutyl acrylate as monomer M2 in an amount of 5 to 70% by weight, particularly 15 to 60% by weight, particularly 20 to 50% by weight, wherein at least the carbon atoms of the isobutyl group in the isobutyl acrylate are of biological origin, and the biocarbon content of the isobutyl acrylate is at least 54 mol%, particularly at least 57 mol%, and iii. Based on the total amount of monomer M, monomer M3 contains or is composed of methyl methacrylate in an amount of 10 to 70% by weight, particularly 20 to 65% by weight, particularly 30 to 62% by weight, iv. Based on the total amount of monomer M, one or more monoethylenically unsaturated monomers M4 selected from acrylic acid, methacrylic acid, itaconic acid and combinations thereof, in an amount of 0.05 to 5% by weight, particularly 0.1 to 4% by weight, particularly 0.5 to 3% by weight, v. One or more nonionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20°C and 1 bar, in amounts of 0 to 9.95% by weight, particularly 0.05 to 5% by weight, particularly 0.1 to 4% by weight, based on the total weight of monomer M, and having a functional group selected from the group consisting of hydroxyalkyl groups, primary carboxamide groups, urea groups, keto groups, and combinations thereof, vi. Based on the total weight of monomer M, one or more monomers M7 in an amount of 0 to 1% by weight, particularly 0 to 0.5% by weight, It consists of, and the total amount of monomers M1 and M3 is in the range of 15 to 90% by weight, particularly 25 to 80% by weight, particularly 35 to 70% by weight, based on the total amount of ethylenically unsaturated monomer M, and the total amount of monomers M1, M2 and M3 is at least 90% by weight, particularly at least 94% by weight, particularly at least 97% by weight, based on the total amount of ethylenically unsaturated monomer M. or, i. Based on the total amount of monomer M, 5 to 50% by weight, particularly 5 to 30% by weight, particularly 5 to 20% by weight, of 1-heptyl acrylate as monomer M1, wherein at least the carbon atoms of the 1-heptyl group in the 1-heptyl acrylate are of biological origin, and particularly the biocarbon content of the 1-heptyl acrylate is at least 63 mol%, particularly at least 69.5 mol%, and ii. Monomer M2 is a mixture of isobutyl acrylate and at least one of n-butyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate in an amount of 5 to 70% by weight, particularly 15 to 60% by weight, particularly 20 to 50% by weight, based on the total amount of monomer M, wherein at least the carbon atoms of the isobutyl group in the isobutyl acrylate are of biological origin, and the biocarbon content of the isobutyl acrylate is at least 54 mol%, particularly at least 57 mol%, and monomer M2, iii. Based on the total amount of monomer M, monomer M3 contains or is composed of methyl methacrylate in an amount of 10 to 70% by weight, particularly 20 to 65% by weight, particularly 30 to 62% by weight, iv. Based on the total amount of monomer M, one or more monoethylenically unsaturated monomers M4 selected from acrylic acid, methacrylic acid, itaconic acid and combinations thereof, in an amount of 0.05 to 5% by weight, particularly 0.1 to 4% by weight, particularly 0.5 to 3% by weight, v. One or more nonionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20°C and 1 bar, in amounts of 0 to 9.95% by weight, particularly 0.05 to 5% by weight, particularly 0.1 to 4% by weight, based on the total weight of monomer M, and having a functional group selected from the group consisting of hydroxyalkyl groups, primary carboxamide groups, urea groups, keto groups, and combinations thereof, vi. Based on the total weight of monomer M, one or more monomers M7 in an amount of 0 to 1% by weight, particularly 0 to 0.5% by weight, It consists of, and the total amount of monomers M1 and M3 is in the range of 15 to 90% by weight, particularly 25 to 80% by weight, particularly 35 to 70% by weight, based on the total amount of ethylenically unsaturated monomer M, and the total amount of monomers M1, M2 and M3 is at least 90% by weight, particularly at least 94% by weight, particularly at least 97% by weight, based on the total amount of ethylenically unsaturated monomer M. or, i. Based on the total amount of monomer M, 5 to 50% by weight, particularly 5 to 30% by weight, particularly 5 to 20% by weight, of 1-heptyl acrylate as monomer M1, wherein at least the carbon atoms of the 1-heptyl group in the 1-heptyl acrylate are of biological origin, and particularly the biocarbon content of the 1-heptyl acrylate is at least 63 mol%, particularly at least 69.5 mol%, and ii. Based on the total amount of monomer M, monomer M2 is provided in an amount of 5 to 70% by weight, particularly 15 to 60% by weight, particularly 20 to 50% by weight, which is selected from n-butyl acrylate and combinations of n-butyl acrylate with at least one of isobutyl acrylate, 2-octyl acrylate and 2-ethylhexyl acrylate. iii. Based on the total amount of monomer M, monomer M3 contains or is composed of methyl methacrylate in an amount of 10 to 70% by weight, particularly 20 to 65% by weight, particularly 30 to 62% by weight, iv. Based on the total amount of monomer M, one or more monoethylenically unsaturated monomers M4 selected from acrylic acid, methacrylic acid, itaconic acid and combinations thereof, in an amount of 0.05 to 5% by weight, particularly 0.1 to 4% by weight, particularly 0.5 to 3% by weight, v. One or more nonionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20°C and 1 bar, in amounts of 0 to 9.95% by weight, particularly 0.05 to 5% by weight, particularly 0.1 to 4% by weight, based on the total weight of monomer M, and having a functional group selected from the group consisting of hydroxyalkyl groups, primary carboxamide groups, urea groups, keto groups, and combinations thereof, vi. Based on the total weight of monomer M, one or more monomers M7 in an amount of 0 to 1% by weight, particularly 0 to 0.5% by weight, The material consists of the following, where the total amount of monomers M1 and M3 is in the range of 15 to 90% by weight, particularly 25 to 80% by weight, and particularly 35 to 70% by weight, based on the total amount of ethylenically unsaturated monomer M, and the total amount of monomers M1, M2 and M3 is at least 90% by weight, particularly at least 94% by weight, and particularly at least 97% by weight, based on the total amount of ethylenically unsaturated monomer M.

[0086] Preferably, the copolymer particles contained in the polymer latex have a Z-mean particle size in the range of 30 to 500 nm, particularly 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 value and no particular 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 maximum values ​​or at least one maximum value and at least a prominent shoulder.

[0087] Unless otherwise specified, particle size and particle size distribution are determined by quasi-elastic light scattering (QELS), also known as dynamic light scattering (DLS). The measurement method is described in ISO 13321:1996. The measurement can be performed using a high-performance particle size analyzer (HPPS). For this purpose, a sample of aqueous polymer latex is diluted and the diluent is analyzed. In relation to QELS, the aqueous diluent may have a polymer concentration ranging from 0.001 to 0.5 wt% depending on the particle size. For most purposes, a suitable concentration is 0.01 wt%. However, higher or lower concentrations may be used to achieve an optimal signal / noise ratio. Dilution can be achieved by adding the polymer latex to an aqueous solution of water or a surfactant to avoid aggregation. Typically, dilution is performed by using a 0.1 wt% aqueous solution of a nonionic emulsifier, such as ethoxylated C16 / C18 alkanol (ethoxylation degree 18), as the diluent. Measurement setup: Malvern HPPS, automated, continuous flow cuvette and Gilson autosampler were used. 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 mean value of the secondary cumulant analysis (mean of fitting), i.e., the Z-mean. The "mean of fitting" is the average intensity-weighted hydrodynamic particle size in nm.

[0088] The hydrodynamic particle size can also be determined by hydrodynamic chromatography-fractionation (HDC), as described, for example, in H. Wiese, "Characterization of Aqueous Polymer Dispersions" in Polymer Dispersions and Their Industrial Applications (Wiley-VCH, 2002), pp. 41-73. For further details, please refer to the examples and description below.

[0089] In a particular group of embodiments, the copolymer particles contained in the polymer latex have a Z-mean particle size in the range of 30 to 200 nm, particularly 40 to 150 nm, as determined by QELS. In this particular group of embodiments, the particle size distribution of the copolymer particles contained in the polymer latex is particularly unimodal or nearly unimodal, meaning that the particle size distribution function has a single maximum value.

[0090] The copolymers contained in the polymer particles may form a single phase or different phases if the polymer particles contain different copolymers with respect to their monomer composition. Preferably, the polymer particles contained in the aqueous polymer latex of the present invention include a polymer phase having a glass transition temperature Tg not exceeding 50°C, particularly 40°C or less, particularly 30°C or less, preferably in the range of -40 to +50°C, more preferably in the range of -25 to +40°C, and particularly in the range of -20 to +30°C.

[0091] The glass transition temperature referred to herein is the actual glass transition temperature. The actual glass transition temperature can be experimentally determined by differential scanning calorimetry (DSC) after preparing a sample according to ISO 11357-2:2013, preferably according to ISO 16805:2003.

[0092] 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 emulsion polymerization. The theoretical glass transition temperature is usually calculated from the monomer composition using Fox's equation: 1 / Tg t =x a / Tg a +x b / Tg b +....x n / Tg n ,

[0093] In this equation, x a , x b ,....x nis the mass fraction of monomers a, b, ..., n, and Tg a , Tg b ,....Tg n Tg is the actual glass transition temperature in Kelvin units of a homopolymer synthesized from only one of monomers 1, 2, ..., n at a time. Fox's formula is described by Fox in Bull. Am. Phys. Soc. 1956, 1, page 123, and similarly in Ullmann's Encyclopadie der technischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], vol. 19, p. 18, 4th ed., Verlag Chemie, Weinheim, 1980. The actual Tg values ​​for homopolymers of most monomers are publicly 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 include, for example, J. Brandrup, E. H. Mergut, 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.

[0094] Typically, the theoretical glass temperature Tg is calculated according to Fox as described herein. tThe experimentally determined glass transition temperatures described herein are similar or identical, and do not deviate from each other by more than 5K, and especially not by more than 2K. Therefore, both the actual and theoretical glass transition temperatures of polymer phases (1) and (2) are such that they reach the desired glass transition temperatures Tg(1) and Tg(2), respectively, provided that the monomer composition contains the appropriate monomers Ma, Mb...Mn and their mass fractions x a , x b ,....x n This can be adjusted by selecting the appropriate amount of monomers Ma, Mb...Mn to obtain a copolymer and / or copolymer phase having a desired glass transition temperature, which is common knowledge to those skilled in the art.

[0095] Typically, the copolymer formed by monomer M and contained in the polymer latex of the present invention is film-forming, meaning that copolymer particles form a film when the polymer latex dries. Preferably, the aqueous copolymer latex of the present invention has a minimum film-forming temperature (MFT) of 50°C or less and 40°C or less. MFT is defined as the lowest temperature at which the polymer latex applied to the surface of a substrate forms a uniform, crack-free coating that remains closed after drying (see Ullmann's Encyclopa die der technischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], vol.19, 4th ed., Verlag Chemie, Weinheim, 1980). The minimum film-forming temperature correlates with the lowest glass transition temperature of the copolymer, but is typically somewhat lower, for example, 1 to 5 K lower than the actual glass transition temperature Tg of polymer P. For technical reasons, the MFT cannot be lower than 0°C because the latex typically freezes.

[0096] 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.

[0097] The aqueous polymer dispersions of the present invention generally have a solid content in the range of 30 to 75% by weight, particularly in the range of 40 to 65% by weight, and preferably in the range of 45 to 60% by weight. Solid content represents the proportion of non-volatile matter. The solid content of the dispersion is determined by balancing with infrared moisture analysis. In this determination, a certain amount of the polymer dispersion is introduced into the instrument, heated to 140°C, and then held at that temperature. The measurement procedure is terminated as soon as the average weight loss falls below 1 mg within 140 seconds. The ratio of the weight after drying to the original mass introduced gives the solid content of the polymer dispersion. The total solid content of the formulation is determined arithmetically from the amount of added substances, as well as their solid content and concentration.

[0098] If the polymer in the polymer latex has functional groups complementary to the functional groups of the crosslinking agent, the polymer dispersion may contain a crosslinking agent to achieve post-crosslinking of the polymer latex particles. In this context, the term “complementary” should be understood as meaning that the functional groups of the latex and the functional groups of the crosslinking agent are susceptible to chemical reactions that form chemical bonds between the atoms of each functional group. 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 listed below.

[0099] The aqueous polymer dispersion of the present invention may contain, in addition to the polymer and an optional crosslinking agent, further components conventionally present in aqueous polymer dispersions. These further components may include, for example, surface-active compounds, such as emulsifiers and protective colloids, particularly those used in the production of polymer latex, and further defoaming agents. Further components may include acids, bases, buffers, decomposition products from polymerization reactions, deodorizing compounds, and chain transfer agents. Furthermore, the polymer latex may contain biozides 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 described components typically does not exceed 5% by weight based on the total weight of the polymer latex.

[0100] Preferably, the amount of volatile organic compounds, i.e., the content of organic compounds having a boiling point up to 250°C under standard conditions (101,325 kPa) determined by ISO 17895:2005 by gas chromatography, is less than 0.5% by weight, particularly less than 0.2% by weight, based on the total weight of the polymer latex.

[0101] In addition to the polymer, 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 further water-soluble components. The total concentration of any further components typically does not exceed 10% by weight, particularly 8% by weight, based on the total weight of the aqueous phase.

[0102] The aqueous polymer latex of the present invention can be prepared by any method for preparing an aqueous dispersion of a polymer made from a polymer monomer M. In particular, the aqueous polymer latex of the present invention is prepared by aqueous emulsion polymerization, especially by free radical aqueous emulsion polymerization of monomer M. The term "free radical aqueous emulsion polymerization" means that the polymerization of monomer M is initiated by radicals formed by the breakdown of a polymerization initiator, thereby forming free radicals in the polymerization mixture. Therefore, it is also called "radical-initiated emulsion polymerization". The procedure for radical-initiated emulsion polymerization of monomers in aqueous media is extensively described and is therefore well known to those skilled in the art [see, for this, Emulsion Polymerization in Encyclopedia of Polymer Science and Engineering, Vol. 8, p. 659 (1987); DC. Blackley, High Polymer Latices, Vol. 1, p. 35 (1966); H. Warson, The Applications of Synthetic Resin Emulsions, Chapter 5, p. 246 (1972); D. Diederich, Chemie in unserer Zeit 24, pp. 135-142 (1990); Emulsion Polymerisation, Interscience Publishers, New York (1965); German Patent Application Publication No. 40 03 422; and Dispersionen synthetischer Hochpolymerer, F. Holscher, Springer-Verlag, Berlin (1969)]. Typical procedures for aqueous emulsion polymerization of ethylenically unsaturated monomers are also described in the patent documents discussed in the introduction to this patent application.

[0103] Radical-initiated aqueous emulsion polymerization is typically carried out by emulsifying an ethylenically unsaturated monomer in an aqueous medium that forms an aqueous phase, typically using a surfactant, e.g., an emulsifier and / or protective colloid, and polymerizing this system using at least one initiator, which disintegrates by the formation of a radical, thereby initiating chain-growth addition polymerization of the ethylenically unsaturated monomer 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 to M8 described above. For the purposes of this specification, it will be understood that the process also encompasses seed, step, one-shot, and gradient regimes that are well known to those skilled in the art.

[0104] Aqueous emulsion polymerization initiated by free radicals is initiated by free radical polymerization initiators (free radical initiators). 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, e.g., hydrogen peroxide or peroxodisulfates, e.g., mono- or di-alkali metal or ammonium salts of peroxodisulfate, e.g., mono- and disodium, -potassium or ammonium salts, or organic peroxides, e.g., alkyl hydroperoxides, e.g., tert-butyl hydroperoxide, p-menthyl hydroperoxide or cumyl hydroperoxide, and dialkyl or diaryl peroxides, e.g., 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 redox initiator systems are essentially the peroxides mentioned above. The corresponding reducing agents that can be used are sulfur compounds in a low oxidation state, such as alkali metal sulfites, such as potassium sulfite and / or sodium sulfite; alkali metal bisulfites, such as potassium bisulfite and / or sodium bisulfite; alkali metal metabisulfites, such as potassium metabisulfite and / or sodium metabisulfite; formaldehyde sulfoxylates, such as potassium and / or sodium formaldehyde sulfoxylate; alkali metal salts, specifically potassium and / or sodium salts of aliphatic sulfinic acids and alkali metal hydrogen sulfide, such as potassium hydrogen sulfide and / or sodium hydrogen sulfide; salts of polyvalent metals, such as iron(II) sulfate, ammonium iron(II) sulfate, iron(II) phosphate; enediols, such as dihydroxymaleic acid, benzoin and / or ascorbic acid; and reducing saccharides, such as sorbose, glucose, fructose and / or dihydroxyacetone.

[0105] Preferred free radical initiators are inorganic peroxides, particularly peroxodisulfates.

[0106] Generally, the amount of free radical initiator used based on the total amount of monomer M is 0.05 to 2 pphm, preferably 0.1 to 1 pphm, based on the total amount of monomer M.

[0107] The amount of free radical initiator required for the emulsion polymerization of monomer M can be initially added entirely to the polymerization vessel. However, it is also possible to add any or only a portion of the free radical initiator, for example, 30% by weight or less, particularly 20% by weight or less, 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 supplied to the free radical polymerization reaction under polymerization conditions. The supply of monomer M may be carried out in batches of one or more parts, depending on the consumption, or continuously at a constant or variable flow rate during the free radical emulsion polymerization of monomer M.

[0108] Generally, the term "polymerization conditions" is understood to mean the temperature and pressure at which free radical-initiated aqueous emulsion polymerization proceeds at a sufficient polymerization rate. These conditions depend particularly on the free radical initiator used. Advantageously, the type and amount of free radical initiator, polymerization temperature, and polymerization pressure are chosen so that there is always a sufficient amount of initiating radicals to start or sustain the polymerization reaction.

[0109] Preferably, the radical emulsion polymerization of monomer M is carried out by a so-called supply process (also called a monomer supply method), meaning that at least 80%, particularly at least 90%, or the total amount of monomer M to be polymerized is metered and supplied to the polymerization reaction under polymerization conditions during a metering period P. The addition may be carried out partially, preferably continuously, at a constant or varying supply rate. The duration of period P may depend on the production equipment and can vary, for example, from 20 minutes to 12 hours. Often, the duration of period P is in the range of 0.5 hours to 8 hours, particularly 1 hour to 6 hours. In a multi-stage emulsion polymerization process, the total duration of all steps is typically within the above range. The duration of individual steps is typically shorter. Preferably, at least 70%, particularly at least 80%, particularly at least 90%, or the total amount of polymerization initiator is introduced into the emulsion polymerization in parallel with the addition of monomers.

[0110] Aqueous radical emulsion polymerization is typically carried out in the presence of one or more suitable surfactants. These surfactants typically include emulsifiers, provide micelles in which polymerization takes place, and also help stabilize monomer droplets during aqueous emulsion polymerization and stabilize growing polymer particles. The surfactants used in emulsion polymerization are usually not separated from the polymer dispersion and remain in the aqueous polymer dispersion obtained by the emulsion polymerization of monomer M.

[0111] Surfactants can be selected from emulsifiers and protective colloids. Protective colloids are understood to mean polymer compounds with a molecular weight greater than 2000 Daltons, in contrast to emulsifiers, while emulsifiers typically have lower molecular weights. Surfactants can be anionic, nonionic, or mixtures of nonionic and anionic surfactants.

[0112] Anionic surfactants typically have at least one anionic group, usually selected from phosphate, phosphonic acid, sulfate, and sulfonic acid groups. Anionic surfactants having at least one anionic group are typically used in the form of their alkali metal salts, particularly their sodium salts or their ammonium salts.

[0113] Preferred anionic surfactants are anionic emulsifiers, particularly those having at least one sulfate or sulfonic acid group. Similarly, anionic emulsifiers having at least one phosphate or phosphonic acid group can be used as the sole anionic emulsifier or in combination with one or more anionic emulsifiers having at least one sulfate or sulfonic acid group.

[0114] An example of an anionic emulsifier having at least one sulfate or sulfonic acid group is, for example, Alkyl sulfates, especially C8-C 22 - Alkyl sulfate salts, especially alkali metal salts and ammonium salts, Preferably a sulfate monoester of an ethoxylated alkanol having an ethoxylation level (EO level) in the range of 2 to 40, particularly an ethoxylated C8-C 22 - Salts of monosulfate esters of alkanols, especially alkali metal salts and ammonium salts, Alkyl sulfonic acids, especially C8-C 22 - Alkyl sulfonic acid salts, especially alkali metal salts and ammonium salts, Dialkyl esters, especially diC4-C sulfosuccinates 18 - Alkyl ester salts, especially alkali metal salts and ammonium salts, Alkylbenzenesulfonic acid, especially C4-C 22 - Alkylbenzenesulfonic acid salts, especially alkali metal salts and ammonium salts, and Mono- or disulfonated alkyl-substituted diphenyl ethers, e.g., C4-C on one or both aromatic rings. 24- Salts of bis(phenylsulfonic acid) ethers having alkyl groups, especially alkali metal salts and ammonium salts The latter is general knowledge from, for example, U.S. Patent No. 4,269,749, which is commercially available, for example, Dowfax® 2A1 (Dow Chemical Company). The polymerizable ethylenically unsaturated surfactants having double bonds as described herein, for example, formulas (I) to (IV) (wherein X and Y are SO3, respectively) - Or O-SO3 - It is a compound of ( ).

[0115] Examples of anionic emulsifiers having a phosphate group or phosphonic acid group, including but not limited to the following salts, are selected from the following group: Mono- and dialkyl phosphates, especially C8-C 22 - Alkyl phosphate salts, especially alkali metal salts and ammonium salts, Salts of phosphate monoesters of C2-C3-alkoxylated alkanols, particularly alkali metal salts and ammonium salts, preferably having an alkoxylation level in the range of 2 to 40, and especially in the range of 3 to 30, for example, ethoxylated C8-C2-C3 alkanols, preferably having an ethoxylation level (EO level) in the range of 2 to 40. 22 - A phosphate monoester of an alkanol, preferably having a propoxylation level (PO level) in the range of 2 to 40, propoxylated C8-C 22 - A phosphate monoester of an alkanol, and preferably having an ethoxylation level (EO level) in the range of 1 to 20 and a propoxylation level of 1 to 20, ethoxylated copropoxylated C8-C 22 - Alkanol phosphate monoester, Alkylphosphonic acids, especially C8-C 22 - Alkylphosphonic acid salts, especially alkali metal salts and ammonium salts, and Alkylbenzenephosphonic acids, especially C4-C 22 - Alkylbenzenephosphonic acid salts, especially alkali metal salts and ammonium salts, Surfactants having a polymerizable ethylenically unsaturated double bond described in this specification, for example, compounds of formulas (I) to (IV) (wherein X and Y are each HPO3 - 、PO3 2 、O-HPO3 - or O-PO3 2 ).

[0116] Anionic emulsifiers may also include emulsifiers having a polymerizable double bond, such as emulsifiers of formulas (I) to (IV) and salts thereof, particularly alkali metal salts or ammonium salts thereof.

Chemical formula

[0117] In formula (I), R 1 is H, C1-C 20 -alkyl, C5-C 10 -cycloalkyl, phenyl optionally substituted with C1-C 20 -alkyl, R 2 and R 2’ are both H or together are O, R 3 and R 4 are H or methyl, m is 0 or 1, n is an integer from 1 to 100, and X is SO3 - 、O-SO3 - 、O-HPO3 - or O-PO3 2- .

Chemical formula

[0118] In formula (II), R is H, C1-C 20 -alkyl, C5-C 10 -cycloalkyl, phenyl optionally substituted with C1-C 20 -alkyl, k is 0 or 1, and X is SO3 - 、O-SO3 - 、O-HPO3 - or O-PO3 2- . [ka]

[0119] In equation (III), R 1 H, C1-C 20 -alkyl, O-C1-C 20 -alkyl, C5-C 10 -Cycloalkyl, O-C5-C 10 -Cycloalkyl, C1-C 20 -O-phenyl which may be substituted with alkyl, n is an integer from 1 to 100, and Y is SO3 - HPO3 - or PO3 2- That is the case. [ka]

[0120] In equation (IV), R 1 H, C1-C 20 -Alkyl or 1-phenylethyl, R 2 H, C1-C 20 - is alkyl or 1-phenylethyl, A is C2-C4-alkanediyl, e.g., 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- That is the case.

[0121] Specific embodiments of the copolymerizable emulsifier of formula (I) are referred to as sulfate or phosphate esters of polyethylene glycol monoacrylate. Similarly, specific embodiments of the copolymerizable emulsifier of formula (I) may also be referred to as phosphonate or allyl ether sulfates of polyethylene glycol monoacrylate. Commercial copolymerizable emulsifiers of formula (I) include Maxemul® emulsifier, Sipomer® PAM emulsifier, Latemul® PD, and ADEKA Reasoap® PP-70.

[0122] A specific embodiment of the copolymerizable emulsifier of formula (II) is also called alkylallyl sulfosuccinate. A commercially available copolymerizable emulsifier of formula (II) is Trem® LF40.

[0123] Certain embodiments of the copolymerizable emulsifier of formula (III) are also referred to as branched unsaturated. Commercial copolymerizable emulsifiers of formula (III) include Adeka® Reasoap emulsifier and Hitenol® KH.

[0124] Specific embodiments of the copolymerizable emulsifier of formula (IV) are also referred to as polyoxyethylene alkylphenyl ether sulfate and polyoxyethylene mono- or distylylphenyl ether sulfate. Commercial copolymerizable emulsifiers of formula (IV) are Hitenol® BC and Hitenol® AR emulsifiers.

[0125] 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.

[0126] Preferably, the surfactant comprises at least one anionic emulsifier having at least one sulfate or sulfonic acid group. At least one anionic emulsifier having at least one sulfate or sulfonic acid group may be the only type of anionic emulsifier. However, a mixture of at least one anionic emulsifier having at least one sulfate or sulfonic acid group and at least one anionic emulsifier having at least one phosphate or phosphonic acid group may also be used. In such a mixture, the amount of at least one anionic emulsifier having at least one sulfate or sulfonic acid group is preferably at least 50% by weight based on the total weight of the anionic surfactant used in the method of the present invention. In particular, the amount of the anionic emulsifier having at least one phosphate or phosphonic acid group does not exceed 20% by weight based on the total weight of the anionic surfactant used in the method of the present invention.

[0127] Preferred anionic surfactants are anionic emulsifiers selected from the following group (including mixtures thereof): Alkyl sulfates, especially C8-C 22 - Alkyl sulfate salts, especially alkali metal salts and ammonium salts, Sulfate monoesters of ethoxylated alkanols, preferably having an ethoxylation level (EO level) in the range of 2 to 40, particularly ethoxylated C8-C 22 - Salts of monosulfate alkanols, especially alkali metal salts, Sulfuric acid monoesters of ethoxylated alkylphenols, particularly ethoxylated C4-C 18 -Sulfuric acid monoester of alkylphenol (EO level, preferably 3 to 40), Alkylbenzenesulfonic acid, especially C4-C 22 -Alkylbenzenesulfonic acid, Mono- or disulfonated alkyl-substituted diphenyl ethers, e.g., C4-C on one or both aromatic rings. 24 - Bis(phenylsulfonic acid) ethers having an alkyl group. A polymerizable emulsifier of formula (III).

[0128] Anionic emulsifiers selected from the following group (including mixtures thereof) are particularly preferred: Alkyl sulfates, especially C8-C 22 - Alkyl sulfate salts, especially alkali metal salts and ammonium salts, Sulfate monoesters of ethoxylated alkanols, preferably having an ethoxylation level (EO level) in the range of 2 to 40, particularly ethoxylated C8-C 22 - Salts of monosulfate alkanols, especially 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 an alkyl group, Equation (III) (where Y is SO3) - A polymerizable emulsifier.

[0129] Similar to the anionic surfactants described above, the surfactant may also contain one or more nonionic surfactants selected particularly from nonionic emulsifiers. Suitable nonionic emulsifiers include, for example, aromatic aliphatic or aliphatic nonionic emulsifiers, such as ethoxylated mono-, di-, and trialkylphenols (EO level: 3 to 50, alkyl group: C4-C 10 ), ethoxylates of long-chain alcohols (EO level: 3 to 100, alkyl group: C8-C 36 These include ), as well as homopolymers and copolymers of polyethylene oxide / polypropylene oxide. These may contain alkylene oxide units copolymerized in a random distribution or in block form. A very preferred example is EO / PO block copolymer. Ethoxylates of long-chain alkanols, particularly alkyl groups C8-C 30 Preferably, the C has an average ethoxylation level of 5 to 100, and among these, linear C 12 -C 20 Alkyl compounds and those having an average ethoxylation level of 10 to 50 are particularly preferred, and ethoxylated monoalkylphenols are also preferred.

[0130] The surfactant used in the method of the present invention typically comprises 30% by weight or less, particularly 20% by weight or less, of nonionic surfactants, based on the total amount of surfactants used in the method of the present invention, and does not particularly contain 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.

[0131] Preferably, the surfactant is used in an amount such that the amount of the surfactant is in the range of 0.2 to 5% by weight, particularly 0.3 to 4.5% by weight, based on the monomer M being polymerized. In multi-step emulsion polymerization, the surfactant is used in an amount such that the amount of the surfactant is usually in the range of 0.2 to 5% by weight, particularly 0.3 to 4.5% by weight, based on the total amount of monomer polymerized in each step.

[0132] Preferably, the majority of the surfactants used, i.e., at least 80%, are added to the emulsion polymerization in parallel with the addition of monomers. In particular, the monomers are added as an aqueous emulsion to the polymerization reaction containing at least 80% of the surfactants used in the emulsion polymerization.

[0133] It has been found to be advantageous to carry out free radical emulsion polymerization of monomer M in the presence of a seed latex. The seed latex is a polymer latex present in the aqueous polymerization medium before the polymerization of monomer M is initiated. The seed latex may help to better adjust the particle size or the final polymer latex obtained in the free radical emulsion polymerization of the present invention.

[0134] Basically, all polymer latex can function as seed latex. For the purposes of the present invention, seed latex with relatively small polymer particle size is preferred. In particular, the Z-mean particle size of the polymer particles of the seed latex, as determined by dynamic light scattering (DLS) at 20°C (see below), is preferably in the range of 10 to 80 nm, and especially 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 - Alkyl esters, particularly ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethyl-hexyl acrylate, C1-C4-alkyl methacrylate, e.g., methyl methacrylate, monoethylenically unsaturated nitriles, e.g., acrylonitrile, and vinyl aromatic monomers as defined above, e.g., styrene and mixtures thereof, are used to produce ethylenically unsaturated monomers containing one or more monomers selected from this group. In particular, the polymer particles of seed latex are produced from ethylenically unsaturated monomers containing at least 95% by weight of C1-C4-alkyl methacrylate, e.g., methyl methacrylate, monoethylenically unsaturated nitriles, e.g., acrylonitrile, and vinyl aromatic monomers as defined above, e.g., styrene and mixtures thereof, based on the total weight of the monomers forming the seed latex.

[0135] Therefore, seed latex is usually added to the polymerization vessel before the polymerization of monomer M begins. In particular, polymerization conditions are established by adding seed latex to the polymerization vessel and then, for example, heating the mixture to the polymerization temperature. It may be beneficial to add at least a portion of the free radical initiator to the polymerization vessel before starting the addition of monomer M. However, it is also possible to add monomer M and the free radical polymerization initiator to the polymerization vessel in parallel.

[0136] The amount of seed latex calculated as a solid is often in the range of 0.01 to 10% by weight, preferably in the range of 0.05 to 5% by weight, and particularly in the range of 0.05 to 3% by weight, based on the total weight of monomers in the monomer composition M being polymerized.

[0137] 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. Since 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, the polymerization temperature may exceed 100°C and may not exceed 170°C. Polymerization of monomers is usually carried out at ambient pressure, but may be carried out under high pressure. In this case, the pressure can be 1.2, 1.5, 2, 5, 10, 15 bar (absolute) or even higher. When emulsion polymerization is carried out under reduced pressure, pressures of 950 millibars, often 900 millibars, and often 850 millibars (absolute) are established. Advantageously, the free radical aqueous emulsion polymerization of the present invention is carried out at ambient pressure (about 1 atm) with oxygen excluded, for example, under an inert gas atmosphere, for example, nitrogen or argon.

[0138] The process for producing the polymer latex of the present invention may be single-stage polymerization or multi-stage emulsion polymerization. In single-stage polymerization, the total composition of monomers M supplied to the polymerization reaction under polymerization conditions remains the same or nearly the same. In multi-stage emulsion polymerization, the total composition of monomers M supplied to the polymerization reaction under polymerization conditions is changed at least once, in particular, such that the stoichiometric glass transition temperature of the polymer formed in one stage differs from the stoichiometric glass transition temperature of the polymer formed in another stage by at least 10°C, particularly at least 20°C or at least 40°C.

[0139] In a particular group of embodiments, the process of the present invention is carried out as a two-step emulsion polymerization, i.e., the composition of monomers supplied to the polymerization reaction under polymerization conditions is corrected once, or as a three-step or four-step emulsion polymerization, i.e., the composition of monomers supplied to the polymerization reaction under polymerization conditions is corrected two or three times.

[0140] Polymerization of monomer M can optionally be carried out in the presence of a chain transfer agent. A chain transfer agent is understood to mean a compound that moves free radicals, reduces the molecular weight of the growing chain, and / or controls the growth of the chain in polymerization. Examples of chain transfer agents include aliphatic and / or aromatic aliphatic halogen compounds, e.g., 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; and organic thio compounds, e.g., primary, secondary, or tertiary aliphatic thiols, e.g., ethanethiol, n-propanthiol, 2-propanthiol, n-butanethiol, 2-butanethiol, 2-methyl-2-propanthiol, n-pentanethiol, 2-pentanethiol, 3-pentanethiol, 2-methyl-2-butanethiol, 3-methyl-2-butanethiol, n-hexanethiol, 2-hexanethiol, 3-hexanethiol, 2-methyl-2-pentanethiol, 3-methyl-2-pentanethiol, 4-methyl-2-pentanethiol 2-methyl-3-pentanethiol, 3-methyl-3-pentanethiol, 2-ethylbutanethiol, 2-ethyl-2-butanethiol, n-heptanethiol and its isomers, n-octanthiol and its isomers, n-nonanethiol and its isomers, n-decanethiol and its isomers, n-undecanethiol and its isomers, n-dodecanethiol and its isomers, n-tridecanethiol and its isomers, substituted thiols, e.g., 2-hydroxyethanethiol, aromatic thiols, e.g., benzenethiol, ortho-, meta-, or para-methylbenzenethiol, alkyl esters of mercaptoacetic acid (thioglycolic acid), e.g., 2-ethylhexylthioglycolate, alkyl esters of mercaptopropionic acid, e.g., octyl mercaptopropionate, and also, Polymer Handbook, 3rd edition, 1989, J. Brandrup and EHFurther sulfur compounds are described in Immergut, John Wiley & Sons, Section II, pages 133 to 141, as well as aliphatic and / or aromatic aldehydes, e.g., acetaldehyde, propionaldehyde, and / or benzaldehyde; unsaturated fatty acids, e.g., oleic acid; dienes having non-conjugated double bonds, e.g., divinylmethane or vinylcyclohexane; or hydrocarbons having readily abstractable hydrogen atoms, e.g., toluene.

[0141] Alternatively, a mixture of the aforementioned chain transfer agents that do not interfere with each other may be used. Optionally, the total amount of chain transfer agent used in the process of the present invention is generally not more than 2% by weight, and particularly not more than 1% by weight, based on the total amount of monomer M. However, during a particular period of the polymerization reaction, the amount of chain transfer agent added to the polymerization reaction may exceed 2% by weight, be as much as 8% by weight, and particularly not more than 4% by weight, based on the total amount of monomer M added to the polymerization reaction during that period.

[0142] It is often advantageous to post-treat the aqueous polymer dispersion obtained upon completion of monomer M polymerization to reduce the residual monomer content. This post-treatment is carried out chemically, for example, by completing the polymerization reaction using a more effective free radical initiator system (known as post-polymerization), and / or physically, for example, by stripping the aqueous polymer dispersion with vapor or inert gas. Corresponding chemical and physical methods are well known to those skilled in the art; see, for example, European Patent Publication No. 771328, German Patent Publication No. 19624299, German Patent Publication No. 19621027, German Patent Publication No. 19741184, German Patent Publication No. 19741187, German Patent Publication No. 19805122, German Patent Publication No. 19828183, German Patent Publication No. 19839199, German Patent Publication No. 19840586, and German Patent Publication No. 19847115. The combination of chemical and physical post-treatment has the advantage of removing not only unconverted ethylenically unsaturated monomers but also other destructive volatile organic compounds (VOCs) from the aqueous polymer dispersion.

[0143] Since the polymer contained in the aqueous polymer dispersion may contain monomer M4 and, optionally, acidic groups from the polymerization initiator, the aqueous polymer dispersion obtained by the process of the present invention is often neutralized before being formulated as a coating composition. Neutralization of the acidic groups of the polymer is achieved by neutralizing agents known to those skilled in the art after polymerization and / or during polymerization. For example, the neutralizing agent may be added by co-supply with the monomer being polymerized or by a separate supply. Suitable neutralizing agents include organic amines, alkali hydroxides, and ammonium hydroxide. In particular, neutralization is achieved by using ammonia or alkali hydroxides, such as sodium hydroxide or potassium hydroxide.

[0144] Furthermore, it may be preferable to incorporate the polymer latex of the present invention with a post-curing agent. Ideally, such a post-curing agent, also called a post-crosslinking agent, brings about a crosslinking reaction during and / or after film formation by forming coordination bonds or covalent bonds with reactive sites on the surface of the polymer particles.

[0145] Suitable crosslinking agents for providing post-crosslinking are, for example, compounds having at least two functional groups selected from oxazoline, amino, aldehyde, aminooxy, carbodiimide, azilidinyl, epoxy, and hydrazide groups, derivatives or compounds having an acetoacetyl group. These crosslinking agents react with reaction sites of polymers in polymer dispersions having 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.

[0146] Since the polymer contained in the polymer dispersion of the present invention has carboxyl groups, post-crosslinking can be achieved by compounding 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, European Patent No. 0277,361, European Patent No. 0507,407, European Patent No. 0628,582, U.S. Patent No. 5,352,400, U.S. Patent Application Publication No. 2011 / 0151128, and U.S. Patent Application Publication No. 2011 / 0217471. The crosslinking is assumed to be based on the reaction between the carboxyl groups of the polymer and the polycarbodiimides. This reaction typically results in covalent crosslinking primarily based on N-acylurea bonds (JW.Taylor and D.Bassett, E.J.Glass (eds.), Technology for Waterborne Coatings, ACS Symposium Series 663, Am. Chem. Soc., Washington, DC, 1997, Chapter 8, pp. 137-163).

[0147] Similarly, since the polymer particles contained in the polymer dispersion of the present invention have carboxyl groups derived from monomer M4, a suitable post-curing agent may also be a water-soluble or water-dispersible polymer having oxazoline groups, such as those described in U.S. Patent No. 5,300,602 and International Publication No. 2015 / 197662.

[0148] Post-crosslinking can also be achieved in a manner similar to that described in European Patent No. 1227116, which describes an aqueous two-component coating composition containing a binder polymer having carboxylic acid and hydroxyl functional groups, as well as a polyfunctional crosslinking agent having functional groups selected from isocyanates, carbodiimides, aziridinyls, and epoxy groups.

[0149] If the polymer in the polymer dispersion has a keto group, for example, by using monomer M5c, such as diacetone acrylamide (DAAM), post-crosslinking can be achieved by compounding the aqueous polymer dispersion with one or more dihydrazides, particularly aliphatic dicarboxylic acids, such as adipic acid dihydrazides (ADDH) as described in U.S. Patent No. 4,931,494, U.S. Patent Publication No. 2006 / 247367, and U.S. Patent Publication No. 2004 / 143058. These components primarily react during and after film formation, although some preliminary reactions may occur.

[0150] Other suitable agents for achieving post-hardening include: Epoxysilanes that crosslink carboxyl groups in polymers, Dialdehydes, for example, glyoxals for crosslinking urea groups or acetoacetoxy groups, for example, monomers M5b and M5c as defined herein, particularly those derived from 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, such as 4-methoxybenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, acetophenone, e.g., 2-hydroxy-2,2-dimethylacetophenone, 2-phenyl-2,2-dimethylacetophenone, cycloalkylphenyl ketones, e.g., 1-benzoylcyclohexane-1-ol (=1-hydroxycyclohexylphenyl ketone), and benzoin, and mixtures thereof, particularly liquid mixtures, e.g., mixtures of 4-methylbenzophenone and benzophenone, mixtures of 2,4,6-trimethylbenzophenone and benzophenone, and mixtures of 1-hydroxycyclohexylphenyl ketone and benzophenone, e.g., benzophenone. These are some examples.

[0151] Suitable systems are described, for example, in European Patent No. 355028, European Patent No. 441221, European Patent No. 0789724, U.S. Patent No. 5516453 and U.S. Patent No. 5498659, and / or, for example, UV initiators made of Omnirad and IGM Resins (e.g., Esacure TZM, Esacure TZT, Omnirad 4MBZ) are commercially available.

[0152] The present invention also, a) A binder polymer in the form of an aqueous polymer latex as defined herein, b) A water-based coating composition comprising at least one additional component that is not a binder and has been conventionally used in such compositions, This relates to an aqueous coating composition containing [a specific ingredient].

[0153] The aqueous coating composition of the present invention may be formulated as a clear coat or a paint. In the latter case, the aqueous coating composition comprises at least one inorganic pigment that imparts a white shading or color to the coating obtained when the aqueous coating composition is used on a coating substrate.

[0154] The pigments for the purposes of this invention are substantially insoluble, finely dispersed, organic or preferably inorganic colorants as defined in German standard DIN 55944:2003-11. Examples of pigments include, in particular, inorganic pigments, such as white pigments like titanium dioxide (CI Pigment White 6), but also colored pigments, for example, Black pigments, for example, iron oxide black (CI Pigment Black 11), iron manganese black, spinel black (CI Pigment Black 27), carbon black (CI Pigment Black 7), Coloring pigments, e.g., chromium oxide, chromium oxide hydrate green; chromium 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 reed (CI Pigment Red 101); cadmium sulfoselenide (CI Pigment Red 108); molybdate reed (CI Pigment Red 104); ultramarine reed, Iron oxide brown, mixed brown, spinel phase and corundum phase (CI Pigment Brown 24, 29 and 31), chrome orange, Iron oxide yellow (CI Pigment Yellow 42); nickel titanium yellow (CI Pigment Yellow 53; CI Pigment Yellow 157 and 164); chromium titanium yellow; cadmium sulfide and cadmium zinc sulfide (CI Pigment Yellow 37 and 35); chromium yellow (CI Pigment Yellow 34), zinc yellow, alkaline earth metal chromate; naple yellow; bismuth vanadate (CI Pigment Yellow 184); Interference pigments, for example, metallic effect pigments based on coated metal plates, pearlescent pigments based on mica plates coated with metal oxides, and liquid crystal pigments. That is the case.

[0155] Water-based coating compositions may also contain one or more fillers. Examples of suitable fillers include aluminosilicates, e.g., feldspar; silicates, e.g., kaolin, talc, mica, and magnesite; alkaline earth metal carbonates, e.g., calcium carbonate in the form of calcite or chalk; magnesium carbonate; dolomite; and alkaline earth metal sulfates, e.g., calcium sulfate and silicon dioxide. In the coating compositions of the present invention, finely powdered fillers are naturally preferred. Fillers may be used in the form of individual components. However, in practice, filler mixtures, e.g., calcium carbonate / kaolin, calcium carbonate / talc, have been found to be particularly useful. Glossy coatings generally contain only a small amount of very finely powdered filler, or no filler at all. Other fillers include matting agents that significantly impair gloss as desired. Matting agents are generally transparent and may be organic or inorganic. Examples of matting agents include inorganic silicates, such as the Syloid® brand from WRGrace & Company and the Acematt® brand from Evonik GmbH. Organic matting agents are available, for example, under the Ceraflour® and Ceramat® brands from BYK-Chemie GmbH, and under the Deuteron MK® brand from Deuteron GmbH.

[0156] The proportions of pigment and filler in a water-based coating composition can be described by known means using the pigment volume concentration (PVC). PVC is expressed as a percentage of the ratio of the volumes of pigment (VP) and filler (VF) to the total volume of binder (VB), pigment (VP), and filler (VF) in the dry coating film: PVC[%] = (VP + VF) × 100 / (VP + VF + VB).

[0157] When water-based coating compositions are formulated as paints, they typically have a pigment volume concentration (PVC) of at least 5%, particularly at least 10%, and typically not exceeding 90%, particularly 85%. In a preferred group of embodiments, the PVC does not exceed a value of 60%, particularly 50%, specifically in the range of 5 to 60% or 5 to 50%. However, the effects of the present invention on polymer dispersions also appear in varnishes, typically based on varnishes, which have a pigment / filler content of less than 5% by weight and correspondingly less than 5% PVC. In yet another group of embodiments, the PVC is in the range of over 60% to 90%, particularly in the range of 65% to 85%.

[0158] According to one set of embodiments, the aqueous coating compositions of the present invention are designed as coatings containing a white pigment, i.e., they contain at least one white pigment and optionally one or more fillers. As the white pigment, they contain, optionally, rutile-type titanium dioxide in combination with one or more fillers. Particularly preferably, the coating compositions of the present invention contain, for example, one or more fillers, e.g., chalk, talc, or mixtures thereof, preferably a rutile-type white pigment, more specifically titanium dioxide.

[0159] In another preferred group of embodiments, the aqueous coating compositions of the present invention are designed as clear coats or wood stain formulations. In contrast to paints, clear coats are essentially free of pigments and fillers, while wood stains contain very few fillers, i.e., less than 5% PVC.

[0160] According to a particular group of embodiments, the present invention also, i) At least one aqueous polymer latex as defined above, ii) Titanium dioxide pigment, This invention relates to an aqueous coating composition containing (hereinafter also referred to as an aqueous coating composition).

[0161] According to a further specific group of embodiments, the present invention also relates to the use of aqueous polymer latex as a binder in aqueous coating compositions containing titanium dioxide pigment.

[0162] In the embodiments described above, the aqueous polymer latex is combined with a TiO2 pigment slurry or paste. The TiO2 concentration of the aqueous TiO2 pigment slurry or paste used to prepare the aqueous coating composition is generally in the range of 30% to 85% by weight, often 40% to 80% by weight, in any case based on the total weight of the aqueous TiO2 pigment slurry or paste. The titanium dioxide pigment used to prepare the aqueous dispersion of the pigment slurry or paste can be any TiO2 pigment conventionally used in coating compositions, particularly aqueous coating compositions. Often, a TiO2 pigment is used, and the TiO2 particles are preferably of the rutile type. In another preferred embodiment, the TiO2 particles may also be coated with, for example, aluminum, silicon, and zirconium compounds.

[0163] 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; particularly more preferably, the weight ratio of polymer to titanium dioxide pigment is in the range of 0.5:3.0 to 3.0:0.5, and especially in the range of 0.5:1.5 to 1.5:0.5.

[0164] 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.

[0165] Generally, aqueous coating compositions further include at least one additive selected from the group consisting of thickeners, defoamers, leveling agents, film-forming aids, biocides, wetting agents or dispersants, fillers, and binders.

[0166] Aqueous coating compositions can be easily prepared by mixing TiO2 pigment powder or an aqueous slurry or paste of TiO2 pigment with the aqueous polymer latex of the present invention, preferably by shearing the mixture, for example by using a dissolving machine conventionally used for preparing water-based paints. It is also possible to prepare an aqueous slurry or paste of the TiO2 pigment and the aqueous polymer latex of the present invention and incorporate or mix it with further polymer latex of the present invention or any other polymer latex binder.

[0167] Aqueous dispersions of polymer composite materials can also be prepared by incorporating the aqueous polymer latex of the present invention as a binder or co-binder into an aqueous base formulation of a paint that already contains a 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.

[0168] To stabilize TiO2 pigment particles in an aqueous pigment slurry or paste, 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 polyphosphate, potassium polyphosphate, or ammonium polyphosphate; alkali metal salts and ammonium salts of acrylic acid homopolymers or copolymers or maleic anhydride polymers; polyphosphonates, such as sodium 1-hydroxyethane-1,1-diphosphonate and naphthalene sulfonates, particularly their sodium salts.

[0169] The polymer concentration of the aqueous polymer latex used to prepare aqueous dispersions of polymer composite materials is generally in the range of 10% to 70% by weight, preferably 20% to 65% by weight, and most preferably 30% to 60% by weight, based on the total weight of the aqueous polymer latex in any case.

[0170] In addition to the polymer latex and titanium dioxide pigment and optional elements of the present invention, the aqueous coating composition may contain one or more pigments different from the TiO2 pigment and / or fillers as described above.

[0171] Preferably, the aqueous coating composition comprises at least one aqueous polymer latex as defined herein, and further comprises a rheology modifier. Suitable rheology modifiers include associative thickening polymers and non-associative rheology modifiers. The aqueous liquid composition preferably comprises a thickening agent selected from the group consisting of associative thickening agents, non-associative thickening agents, and combinations thereof.

[0172] Associative thickening polymers are well known and are frequently described in scientific literature, for example, E.S. Challer et al., "Associative Thickeners," Handbook of Coating Additives, Vol. 2 (editor L.J. Calbo), Marcel Decker pp. 192, 105-164, and J. Bielemann, "PUR-Verdicker," Additives for Coatings (editor J. Bielemann), Wiley 2000, pp. 50-58. HEUR and HMPE type NiSAT thickening polymers are also described in patent documents, for example, U.S. Patent No. 4,079,028, U.S. Patent No. 4,155,892, European Patent No. 61822, European Patent No. 307775, International Publication No. 96 / 31550, European Patent No. 612329, European Patent No. 1013264, European Patent No. 1541643, European Patent No. 1584331, European Patent No. 2184304, German Patent No. 4137247, German Patent No. 102004008015, German Patent No. 102004031786, U.S. Patent Application Publication No. 2011 / 0166291, and International Publication No. 2012 / 052508. Separately, associative thickening polymers are commercially available.

[0173] Associative thickening polymers include anionic acrylate-type thickening polymers, so-called HASE polymers (hydrophobic modified polyacrylate thickeners), which are copolymers of acrylic acid monomers and alkyl acrylate monomers, where the alkyl group of the alkyl acrylate may have 6 to 24 carbon atoms. Associative thickening 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, in particular a polyether moiety, in particular at least one polyethylene oxide moiety and two or more terminal hydrocarbon groups, each having at least 4 carbon atoms, in particular 4 to 24 carbon atoms, e.g., 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 hydrophobic modified polyethylene oxide urethane rheology modifiers, also called HEUR or PUR thickeners, and hydrophobic modified polyethylene oxide, also called HMPE.

[0174] The amount of associative thickening polymer depends on the desired viscosity profile and is often in the range of 0.05 to 2.5% by weight, particularly 0.1 to 2% by weight, and especially 0.2 to 2% by weight, based on the latex coating.

[0175] Suitable non-associative rheological modifiers include cellulosic thickeners, particularly hydroxyethylcellulose, but also acrylate emulsion (ASE)-based thickeners. Among non-associative rheological modifiers, non-associative cellulosic thickeners are preferred.

[0176] The total amount of thickening polymer depends on the desired viscosity profile and is often in the range of 0.05 to 6% by weight, particularly 0.1 to 5.5% by weight, and especially 0.15 to 5% by weight, based on the latex coating.

[0177] The aqueous coating composition of the present invention may also contain conventional additives. Conventional additives depend on the type of coating, as is well known. a wetting agent or a dispersing agent, a film-forming aid, also called a fusing agent, a leveling agent, a UV stabilizer, a biocide, and an antifoaming agent / defoaming agent are mentioned, but are not limited thereto.

[0178] Suitable wetting agents or dispersing agents are, for example, sodium polyphosphate, potassium polyphosphate or ammonium polyphosphate, alkali metal salts and ammonium salts of acrylic acid copolymers or maleic anhydride copolymers, polyphosphonates, for example sodium 1-hydroxyethane-1,1-diphosphonate and naphthalene sulfonates, especially their sodium salts.

[0179] Suitable film-forming aids are solvents and plasticizers. Plasticizers, in contrast to solvents, 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 film-forming aids are, 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, for example commercially available under the names Solvenon®, Lusolvan® and Loxanol® from BASF SE, and under the trade name Dowanol® from Dow. The amount is preferably less than 5% by weight, more preferably less than 1% by weight, based on the total formulation. Formulation without a film-forming aid is also completely possible. In many cases, the coating composition does not require any film-forming aid.

[0180] Further suitable additives and components are described, for example, by J. Bieleman, "Additives for Coatings," Whiley-VCH, Weinheim 2000; by TCPatton, "Paint Flow and Pigment Dispersions," 2nd edition, John Whiley & Sons 1978; and by M. Schwartz and R. Baumstark, "Water-based Acrylates for Decorative Coatings," Curt R. Vincentz Verlag, Hanover 2001.

[0181] The aqueous coating composition of the present invention may also be formulated as a low-VOC coating. In this case, the concentration of the volatile compound in the coating composition is preferably less than 0.1% by weight, more preferably less than 0.05% by weight, based on the total amount of the aqueous coating composition. The volatile compound according to the present invention is a compound having a boiling point of less than 250°C at 10¹³ millibars.

[0182] The water-based coating composition of the present invention is particularly useful for architectural coatings, i.e., for coating the exterior or interior of buildings. In this case, the substrate may be a mineral substrate, such as plaster, gypsum, plasterboard or concrete, wood, wood-based material, metal, wallpaper, or plastic, such as PVC.

[0183] The aqueous coating composition can be applied to a substrate to be coated by conventional methods, such as by spraying, dipping, rolling, or bar coating, for example, by applying with a brush or roller. The preferred application method is by brush and / or roller.

[0184] Typically, the coating of a substrate is carried out by first coating the substrate with the aqueous coating composition of the present invention, and then subjecting the aqueous coating thus obtained to a drying process in a temperature range particularly between -10°C and +50°C, preferably between +5°C and +40°C, and especially preferably between +10°C and +35°C.

[0185] Substrates coated with the aqueous coating composition of the present invention have excellent resistance to whitening when exposed to water or weathering conditions. Furthermore, the coating has good adhesive properties, such as high dry alkyd adhesion, good opacity, high block resistance, good stain removal properties, high moisture scrub resistance, and low stain adhesion.

[0186] The present invention also, a) A binder polymer in the form of an aqueous polymer latex as defined herein, b) A water-based adhesive composition comprising at least one additional component that is not a binder and has been conventionally used in such compositions, This relates to a water-based adhesive composition containing [specific ingredient].

[0187] The aqueous adhesive compositions of the present invention typically contain, in addition to the polymer latex, two or more additional components, such as additives, that are well known in the art, including but not limited to, rheological modifiers, plasticizers, tackifiers, defoamers, wetting agents, biocides, and adhesion promoters, and the rheological modifiers, plasticizers, defoamers, wetting agents, and biocides may be selected from those described herein. The aqueous adhesive compositions of the present invention may also contain further or other additional components that are well established in the art. Formulations of the aqueous adhesive compositions of the present invention suitable for a particular adhesive application contain a certain amount of a specific binder polymer and at least one, usually two or more, specific additional components. The exact properties and amounts of all these components useful for preparing such formulations can usually be determined by methods known to themselves. [Modes for carrying out the invention]

[0188] Examples The present invention should be illustrated by the following non-limiting examples.

[0189] 1. Abbreviations: MeHQ 4-methoxyphenol (hydroquinone monomethyl ether) wt%: weight %

[0190] Here, and hereinafter, the terms "room temperature" and "ambient temperature" mean a temperature in the range of 22 to 23 °C.

[0191] 2. Analysis of polymer latex 2.1 Solids content The solids content was determined by drying a specified amount of the aqueous polymer dispersion (about 2 g) in an aluminum crucible having an inner diameter of about 5 cm at 130 °C in a drying cabinet (for 2 hours) until a constant weight was reached. Two separate measurements were carried out. The values reported in the examples are each the average of the two measured values.

[0192] 2.2 Particle size Unless otherwise specified, the average particle size of the polymer latex was determined by the above-mentioned dynamic light scattering (DLS) using Malvern HPPS.

[0193] 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) using a DSC instrument (Q 2000 series manufactured by TA instruments).

[0194] 2.4 pH measurement The pH measurement was carried out on the reaction mixture using a pH meter.

[0195] 3. Components The following components are used in this example.

[0196]

Table 1A

[0197] Isobutyl acrylate can be prepared by transesterification of ethyl acrylate with isobutanol, similar to the protocol for producing bioisoamyl acrylate described in International Publication No. 2022 / 018013.

[0198] Protocol for preparing 1-heptyl acrylate: P1: Preparation of 1-heptyl acrylate by transesterification. In a heatable 4 L double-walled glass reactor equipped with a three-stage cross-beam stirrer, thermal elements, column (Montz A3-750 packing), condenser, separator, membrane pump, distillate receiver, and dilute air sparging tube, ethyl acrylate (3205 g), MeHQ (1.59 g), and bio-1-heptanol (1203 g, 10.3 mol) were introduced. 250 g of ethyl acrylate was removed by distillation under dilute air sparging (1 L / h) at a reflux ratio of 6:2 at a pressure of 300 mg / m and a bath temperature of 100 °C. The pressure was then set to 860 mg / m and the bath temperature to 125 °C. 24.1 g of titanium tetraisopropoxylate was added as a catalyst. After boiling began, the azeotropic mixture of ethyl acrylate and ethanol was continuously removed, initially at a reflux ratio of 10:7, and this ratio was varied throughout the reaction. During the reaction, the sump temperature rose to a maximum of 102°C, and the vacuum was adjusted to a maximum of 610 millibars. The progress of the reaction was monitored by taking samples of the distillate and sump at regular intervals. To promote the conversion, additional catalyst (total 34.6 g) was added in fractions during the reaction. After 6.6 hours of distillation, the conversion rate was over 97.5%. The ethyl acrylate was removed by distillation at a bath temperature of 115°C, while gradually reducing the vacuum to 335 millibars. 300 ml of water was added to the reaction mixture, and after stirring at a bath temperature of 100°C for 1 hour, the water was removed by distillation. During distillation, the pressure dropped to 12 millibars. 60 g of Harbolite 900 filter aid was added to the reaction mixture, and it was filtered through a pressure filter funnel.

[0199] After filtration, 1-heptyl acrylate was obtained in a yield of 1350 g (77%) with a GC purity of 94.6 GC area%.

[0200] P2: Preparation of 1-heptyl acrylate by transesterification In a heatable 4 L double-walled glass reactor equipped with a three-stage cross-beam stirrer, thermal elements, column (Montz A3-750 packing), condenser, separator, membrane pump, distillate receiver, and dilute air sparging tube, ethyl acrylate (3033 g), MeHQ (1.50 g), and bio-1-heptanol (1127 g, 9.64 mol) were introduced. 256 g of ethyl acrylate was removed by distillation under dilute air sparging (1 L / h) at a reflux ratio of 6:2 at a pressure of 350 mg / m and a bath temperature of 100 °C. The pressure was then set to 860 mg / m and the bath temperature to 125 °C. 22.4 g of titanium tetraisopropoxylate was added as a catalyst. After boiling began, the azeotrope of ethyl acrylate and ethanol was continuously removed, initially at a reflux ratio of 10:3, and this ratio was varied throughout the reaction. During the reaction, the sump temperature rose to a maximum of 102°C, and the vacuum was adjusted to a maximum of 610 millibars. The progress of the reaction was monitored by taking samples of the distillate and sump at regular intervals. To promote the conversion, additional catalyst (totaling 45.1 g) was added in fractions during the reaction. After 8.8 hours of distillation, the conversion rate was 97.4%. 300 ml of water was added to the reaction mixture, and after stirring at a bath temperature of 100°C for 1 hour, the water and ethyl acrylate were removed by distillation. During distillation, the pressure decreased to 20 millibars. 60 g of Harbolite 900 filter aid was added to the reaction mixture, and it was filtered through a pressure filter funnel.

[0201] After filtration, 1-heptyl acrylate was obtained in a yield of 1265 g (77%) with a GC purity of 94.5 GC area%.

[0202] P3: Preparation of 1-heptylacrylate by esterification In a heatable 4 L double-walled glass reactor equipped with a three-stage cross-beam stirrer, a water separator with a centralized cooler, a thermal element, and a dilute air sparging tube, 650 g of bio-1-heptanol was added. 1.50 g of 12% sodium borohydride solution in 40% NaOH was added and stirred. After 1 hour, 0.48 g of MeHQ, 443 g of pure acrylic acid, 23.02 g of 70% methanesulfonic acid, 0.11 g of copper(I) chloride, 0.53 g of 50% phosphinic acid, and 200 g of cyclohexane were added (in this order). The water separator was filled with cyclohexane. The reaction mixture was heated with stirring and dilute air sparging while the bath temperature was set to 125°C. The azeotropic mixture of cyclohexane and water was removed by distillation at a sump temperature of 90–120°C. During this process, the aqueous phase formed in the water separator was discarded, and the organic phase was transferred back into the reactor. After removing 99 g of water within 8.3 hours, the reaction mixture was cooled to room temperature. The organic phase was extracted first with 450 g of water, then with 260 g of 12.5% ​​NaOH aqueous solution, and finally with 450 g of water. The resulting 1080 g crude solution was mixed with 95 mg of MeHQ and then concentrated in a rotary evaporator at 65°C and 380 mg to 10 mg. The concentrated solution was filtered through a pleated filter.

[0203] 1-Heptylacrylate was obtained in a yield of 876 g (92%) with a GC purity of 97.6% area%.

[0204] 4. Preparation Example 4.1 Binder Examples Example E1 of the present invention Binders based on polymers containing 1-heptyl acrylate and methyl methacrylate 244.3 g of deionized water and 27.3 g of polystyrene seed dispersion (33% by weight, particle size: 30 nm) were added to a reactor equipped with a stirrer, temperature control, nitrogen inlet, and several inlets. The reaction mixture was purged with nitrogen and heated to 85°C. 5.0 g of feed 2 was added at 85°C. After 5 minutes, feed 1 and feed 2 were added over 180 minutes.

[0205] Feed 1: 400.5 g deionized water, 18.5 g Dowfax 2A1, 20.8 g Lutensol TO 82, 6.9 g acrylic acid, 13.9 g acrylamide (50 wt% aqueous solution), 282.6 g 1-Heptylacrylate, 401.2 g of methyl methacrylate. Feed 2: 19.8 g of sodium persulfate aqueous solution (7% by weight).

[0206] The reaction mixture was polymerized at 85°C for 30 minutes. Then, feeds 3 and 4 were added over 60 minutes.

[0207] Feed 3: 6.9 g of t-butyl hydroperoxide aqueous solution (10% by weight). Feed 4: 6.2 g of Longalit C aqueous solution (10% by weight).

[0208] Next, the reaction mixture was cooled to ambient temperature and neutralized with sodium hydroxide to a pH of 8-9. Tg (dry dispersion): 20℃ Average particle size: 140 nm Solid content: 49.3% by weight

[0209] Example E2 of the present invention Binders based on polymers containing 1-heptyl acrylate, isobutyl acrylate, and methyl methacrylate 244.3 g of deionized water and 27.3 g of polystyrene seed dispersion (33% by weight, particle size: 30 nm) were added to a reactor equipped with a stirrer, temperature control, nitrogen inlet, and several inlets. The reaction mixture was purged with nitrogen and heated to 85°C. 5.0 g of feed 2 was added at 85°C. After 5 minutes, feed 1 and feed 2 were added over 180 minutes.

[0210] Feed 1: 400.5 g deionized water, 18.5 g Dowfax 2A1, 20.8 g Lutensol TO 82, 6.9 g acrylic acid, 13.9 g acrylamide (50 wt% aqueous solution), 104.7 g 1-heptyl acrylate, 272.1 g isobutyl acrylate, 307.0 g methyl methacrylate. Feed 2: 19.8 g of sodium persulfate aqueous solution (7% by weight).

[0211] The reaction mixture was polymerized at 85°C for 30 minutes. Then, feeds 3 and 4 were added over 60 minutes.

[0212] Feed 3: 6.9 g of t-butyl hydroperoxide aqueous solution (10% by weight). Feed 4: 6.2 g of Longalit C aqueous solution (10% by weight).

[0213] Next, the reaction mixture was cooled to ambient temperature and neutralized with sodium hydroxide to a pH of 8-9. Tg (dry dispersion): 17℃ Average particle size: 129 nm Solid content: 48.2% by weight

[0214] Example E3 of the present invention Binders based on polymers containing 1-heptyl acrylate, n-butyl acrylate, and methyl methacrylate. 244.3 g of deionized water and 27.3 g of polystyrene seed dispersion (33% by weight, particle size: 30 nm) were added to a reactor equipped with a stirrer, temperature control, nitrogen inlet, and several inlets. The reaction mixture was purged with nitrogen and heated to 85°C. 5.0 g of feed 2 was added at 85°C. After 5 minutes, feed 1 and feed 2 were added over 180 minutes.

[0215] Feed 1: 400.5 g deionized water, 18.5 g Dowfax 2A1, 20.8 g Lutensol TO 82, 6.9 g acrylic acid, 13.9 g acrylamide (50 wt% aqueous solution), 104.7 g 1-heptyl acrylate, 209.3 g n-butyl acrylate, 369.8 g methyl methacrylate. Feed 2: 19.8 g of sodium persulfate aqueous solution (7% by weight).

[0216] The reaction mixture was polymerized at 85°C for 30 minutes. Then, feeds 3 and 4 were added over 60 minutes.

[0217] Feed 3: 6.9 g of t-butyl hydroperoxide aqueous solution (10% by weight). Feed 4: 6.2 g of Longalit C aqueous solution (10% by weight).

[0218] Next, the reaction mixture was cooled to ambient temperature and neutralized with sodium hydroxide to a pH of 8-9. Tg (dry dispersion): 22℃ Average particle size: 132 nm Solid content: 48.9% by weight

[0219] Comparative Example C1 Binders based on polymers containing n-butyl acrylate and methyl methacrylate 244.3 g of deionized water and 27.3 g of polystyrene seed dispersion (33% by weight, particle size: 30 nm) were added to a reactor equipped with a stirrer, temperature control, nitrogen inlet, and several inlets. The reaction mixture was purged with nitrogen and heated to 85°C. 5.0 g of feed 2 was added at 85°C. After 5 minutes, feed 1 and feed 2 were added over 180 minutes.

[0220] Feed 1: 400.5 g deionized water, 18.5 g Dowfax 2A1, 20.8 g Lutensol TO 82, 6.9 g acrylic acid, 13.9 g acrylamide (50 wt% aqueous solution), 346.4 g methyl methacrylate, 332.6 g n-butyl acrylate. Feed 2: 19.8 g of sodium persulfate aqueous solution (7% by weight).

[0221] The reaction mixture was polymerized at 85°C for 30 minutes. Then, feeds 3 and 4 were added over 60 minutes.

[0222] Feed 3: 6.9 g of t-butyl hydroperoxide aqueous solution (10% by weight). Feed 4: 6.2 g of Longalit C aqueous solution (10% by weight).

[0223] Next, the reaction mixture was cooled to ambient temperature and neutralized with sodium hydroxide to a pH of 8-9. Tg (dry dispersion): 21℃ Average particle size: 125 nm Solid content: 48.8% by weight

[0224] 4.1 Formulation example Example E4 of the present invention Formulation of semi-gloss paint containing the binder of Example E1 200.0 g of Kronos 4311 pigment was mixed with 15.0 g of water. At a low stirring 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 a high stirring speed, 1.5 g of Attagel 50 (BASF), 25.0 g of Minex 10 (Sibelco) filler, 125.0 g of Kronos 4311 pigment, 106.3 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 490.7 g of binder from Example E1, 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 compound (Eastman) and 5.0 g of Optifilm 400 compound (Eastman) were added and mixed for 5 minutes. Then, 2.0 g of Proxel AQ biocide (Lonza), 3.0 g of Polyphase 663 fungicide (Troy Corporation), and 2.9 g of Rheolate CVS 10 nonionic associative thickener (Elementis) were added and mixed for 5 minutes. Finally, 1.0 g of Acrysol RM 895 nonionic associative thickener (Dow) was added and the mixture was stirred at medium speed for 30 minutes.

[0225] Example E5 of the present invention Formulation of semi-gloss paint containing binder from Example E2 200.0 g of Kronos 4311 pigment was mixed with 15.0 g of water. At a low stirring 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 a high stirring speed, 1.5 g of Attagel 50 (BASF), 25.0 g of Minex 10 (Sibelco) filler, 125.0 g of Kronos 4311 pigment, 98.1 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 501.9 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 compound (Eastman) and 5.0 g of Optifilm 400 compound (Eastman) were added and mixed for 5 minutes. Then, 2.0 g of Proxel AQ biocide (Lonza), 3.0 g of Polyphase 663 fungicide (Troy Corporation), and 2.0 g of Rheolate CVS 10 nonionic associative thickener (Elementis) were added and mixed for 5 minutes. Finally, 1.7 g of Acrysol RM 895 nonionic associative thickener (Dow) was added and the mixture was stirred at medium speed for 30 minutes.

[0226] Example E6 of the present invention Formulation of semi-gloss paint containing binder from Example E3 200.0 g of Kronos 4311 pigment was mixed with 15.0 g of water. At a low stirring 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 a high stirring speed, 1.5 g of Attagel 50 (BASF), 25.0 g of Minex 10 (Sibelco) filler, 125.0 g of Kronos 4311 pigment, 111.6 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 494.7 g of binder from Example E3, 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 compound (Eastman) and 5.0 g of Optifilm 400 compound (Eastman) were added and mixed for 5 minutes. Then, 2.0 g of Proxel AQ biocide (Lonza), 3.0 g of Polyphase 663 fungicide (Troy Corporation), and 2.0 g of Rheolate CVS 10 nonionic associative thickener (Elementis) were added and mixed for 5 minutes. Finally, 1.0 g of Acrysol RM 895 nonionic associative thickener (Dow) was added and the mixture was stirred at medium speed for 30 minutes.

[0227] Comparative Example C2 Formulation of semi-gloss paint containing binder from Example C1 200.0 g of Kronos 4311 pigment was mixed with 15.0 g of water. At a low stirring 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 a high stirring speed, 1.5 g of Attagel 50 (BASF), 25.0 g of Minex 10 (Sibelco) filler, 125.0 g of Kronos 4311 pigment, 113.1 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 495.7 g of binder from Example C1, 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 compound (Eastman) and 5.0 g of Optifilm 400 compound (Eastman) were added and mixed for 5 minutes. Then, 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 added and mixed for 5 minutes. Finally, 1.0 g of Acrysol RM 895 nonionic associative thickener (Dow) was added and the mixture was stirred at medium speed for 30 minutes.

[0228] 4.3 Coating Characteristics The following coating characteristics were determined.

[0229] Gloss: A coating was prepared on a Leneta 3B black and white shielded drawdown card using a 3-mil drawdown bar. The film was dried at room temperature for 24 hours. Gloss was measured using a gloss meter at angles of 20°, 60°, and 80°, respectively. The results were as follows:

[0230] [Table 2]

[0231] Glossiness is improved in E5 compared to C2.

[0232] Low shear viscosity: The low shear viscosity was measured seven days after preparation according to ASTM D562. The results were as follows:

[0233] [Table 3]

[0234] High shear viscosity: The high shear viscosity was measured according to ASTM D4287 on day 7 after preparation. The results were as follows:

[0235] [Table 4]

[0236] The thickening efficiency is improved in E4, E5, and E6 compared to C2.

[0237] Opacity: A coating was prepared on a Leneta 3B black and white shielded drawdown card using a 3-mil drawdown bar. The film was dried at room temperature for 24 hours. Opacity was determined by spectrophotometry as the ratio of reflected light from the dried coating on the black and white areas of the Leneta card. Opacity indicates the coating's ability to conceal the black surface. The results were as follows:

[0238] [Table 5]

[0239] Opacity is slightly improved in E4, E5, and E6 compared to C2.

[0240] Dry alkyd adhesion: Dry alkyd adhesion was measured according to ASTM D3359. Evaluation was performed after 7 days. Dry alkyd adhesion was rated on a scale of 0 to 5, where 0 = complete film peeling and 5 = film not peeling. The results were as follows:

[0241] [Table 6]

[0242] Dry alkyd adhesion is improved in E4 compared to C2.

[0243] Wet alkyd adhesion: Wet alkyd adhesion was measured according to ASTM D3359. Evaluation was performed after 7 days. Wet alkyd adhesion was rated on a scale of 0 to 5, where 0 = complete film peeling and 5 = no film peeling. The results were as follows:

[0244] [Table 7]

[0245] Wet alkyd adhesion is improved in E4 compared to C2.

[0246] König pendulum stiffness: The hardness of a König pendulum was measured according to ASTM D4366 using aluminum as the coating substrate. Evaluation was performed after 7 days. The following results each reflect the average frequency of three measurements.

[0247] [Table 8]

[0248] Hardness is clearly improved in E4 and E6 compared to C2.

[0249] Stain removal: Stain removal was measured according to ASTM D4828. Coating results from E4, E5, and E6 were comparable to those from C2 for pencil, lipstick, crayon, ballpoint pen, red wine, ketchup, coffee, and mustard (visual inspection).

[0250] Dirt and stains: The mill glaze on the surface of yellow pine wood was rubbed with water and allowed to dry overnight. The substrate was divided into sections according to the number of specimens to be tested. Using a suitable brush, the test paint specimens were applied at a natural spreading rate. The coatings were allowed to cure at room temperature for 4 hours and 24 hours, respectively. Then, half of the coated area was covered with 2 inches of dry dirt (Arizona soil or carpet soil). After letting the panel stand for 15 minutes, the dirt was removed by tilting it vertically and tapping it lightly. The soiled area of ​​each specimen was lightly brushed (15 strokes).

[0251] The amount of fouling on the coatings from E5 and E6 was comparable to that of the coatings from C2, but the amount of fouling on the coatings from E4 was significantly reduced compared to the amount of fouling on the coatings from C2 (visual evaluation).

[0252] Scrub resistance: Scrub resistance was measured according to ASTM D2486. The number of scrubbing cycles until failure occurred was determined.

[0253] [Table 9]

[0254] Compared to coatings from C2, the scrub resistance of coatings from E4, E5, and especially E6 was improved.

Claims

1. An aqueous polymer latex of a copolymer obtained by aqueous emulsion polymerization of an ethylenically unsaturated monomer M, Based on the total amount of monomer M, monomer M1, which is 1-heptyl acrylate, is present in an amount of 5 to 90% by weight. Based on the total amount of monomer M, 0 to 70% by weight of acrylic acid C, excluding tert-butyl acrylate. ２ -C ６ - C of alkyl esters and acrylic acid ８ -C ２０ - C of alkyl esters and methacrylic acid ５ -C ２０ - At least one monomer M2 selected from alkyl esters and mixtures thereof, Based on the total amount of monomer M, 5 to 70% by weight of tert-butyl acrylate, C of methacrylic acid １ -C ４ -alkyl ester, C of acrylic acid ５ -C ２０ -cycloalkyl ester, C of methacrylic acid ５ -C ２０ [[ID=第十二]]-cycloalkyl ester, C of acrylic acid ５ -C ２０ -cycloalkylmethyl ester, C of methacrylic acid ５ -C ２０ -cycloalkylmethyl ester (the cycloalkyl in the above monomer is monocyclic, bicyclic or tricyclic, and one or two non-adjacent CH ２ parts may be replaced by oxygen atoms, the cycloalkyl may be unsubstituted or may have 1, 2, 3 or 4 methyl groups), and at least one monomer M3 selected from monovinyl aromatic monomers, methylene-gamma-butyrolactone, and mixtures thereof, Includes, The total amount of monomers M1 and M2 is in the range of 10 to 90% by weight, based on the total amount of ethylenically unsaturated monomer M, and the total amount of monomers M1, M2, and M3 is at least 90% by weight, based on the total amount of ethylenically unsaturated monomer M. Water-based polymer latex.

2. The aqueous polymer latex according to claim 1, wherein at least the carbon atoms of the 1-heptyl group in the monomer M1 are of biological origin.

3. The aqueous polymer latex according to claim 1 or 2, wherein the monomer M2 is selected from the group consisting of n-butyl acrylate, isobutyl acrylate, 2-octyl acrylate, and 2-ethylhexyl acrylate, and mixtures thereof.

4. The aqueous polymer latex according to claim 3, wherein at least the isobutyl group of isobutyl acrylate and / or the carbon atoms of the 2-octyl group of 2-octyl acrylate are of biological origin.

5. The aqueous polymer latex according to any one of claims 1 to 4, wherein the monomer M3 comprises methyl methacrylate.

6. The aqueous polymer latex according to claim 5, wherein the monomer M3 is selected from methyl methacrylate and a combination of methyl methacrylate and at least one further monomer M3 selected from tert-butyl acrylate, n-butyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, alpha-methylene-gamma-butyrolactone, and styrene.

7. The aqueous polymer latex according to any one of claims 1 to 6, wherein the monomer M further comprises at least one monomer M4 selected from monoethylenically unsaturated monomers having an acidic group.

8. The aqueous polymer latex according to claim 7, wherein the monomer M4 is selected from acrylic acid, methacrylic acid, itaconic acid, and combinations thereof.

9. The aqueous polymer latex according to any one of claims 1 to 8, wherein the monomer M further comprises at least one monoethylene unsaturated nonionic monomer M5 having a solubility in deionized water of at least 60 g / L at 20°C and 1 bar.

10. The aqueous polymer latex according to claim 9, wherein the monomer M5 is selected from the group consisting of nonionic monoethylenically unsaturated monomers having a functional group selected from the group consisting of a hydroxyalkyl group, a primary carboxamide group, a urea group, a keto group, and combinations thereof.

11. The monomer M is i. Based on the total amount of monomer M, 5 to 90% by weight of 1-heptyl acrylate as monomer M1, ii. Based on the total amount of monomer M, at least one monomer M2 in an amount of 0 to 70% by weight, iii. Based on the total amount of monomer M, at least one monomer M3 in an amount of 5 to 70% by weight, iv. Based on the total amount of monomer M, one or more monoethylene unsaturated monomers M4 selected from monoethylene unsaturated monomers having an acidic group, in an amount of 0.05 to 5% by weight, v. Based on the total weight of the monomer M, one or more nonionic monomers M5 having a solubility in deionized water of at least 60 g / L at 20°C and 1 bar, in an amount of 0 to 9.95% by weight, An aqueous polymer latex according to any one of claims 1 to 10, comprising:

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 -40 to +40°C.

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

14. Use of the aqueous polymer latex according to any one of claims 1 to 12 as a binder in an aqueous coating composition or an aqueous adhesive composition.

15. A water-based coating composition, a) A binder copolymer in the form of an aqueous polymer latex according to any one of claims 1 to 12, b) At least one further component that is not a binder and has been conventionally used in aqueous coating compositions, A water-based coating composition containing the following:

16. The coating composition according to claim 15, which is a latex paint, particularly a latex paint for architectural coatings, a wood coating or wood coloring composition, or a latex paint for interior coatings.

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