Polymer dispersions for coatings

Abstract

This invention relates to aqueous polymer dispersions obtainable by free radical aqueous emulsion polymerization of olefinically unsaturated monomers M, wherein the olefinically unsaturated monomers M comprise a) a combination of 0.5 wt% to 5.0 wt% of the following substances based on the total weight of monomers M: a1) at least one monomer Ma1 selected from C2-C6 (meth)acrylate hydroxyalkyl esters; a2) at least one monomer Ma2 selected from monoolefinically unsaturated monosulfonic acids having 2 to 10 carbon atoms and their salts; b1) at least one monomer Mb1 selected from 50 wt% to 75.45 wt% of at least one monomer Mb1 based on the total weight of monomers M, which has a solubility of up to 60 g in deionized water at 25 °C and 1 bar. a) a nonionic monoolefinic unsaturated monomer of / L, and the glass transition temperature Tg of its homopolymer is at least 50°C; b2) at least 24% to 49.45% by weight of at least one monomer Mb2 based on the total weight of monomer M, selected from nonionic monoolefinic unsaturated monomers with a solubility of at most 60 g / L in deionized water at 25°C and 1 bar, and the glass transition temperature Tg of its homopolymer is at most 40°C; c) optionally 0.05% to 2.0% by weight of at least one crosslinking monomer Mc; thereby the aqueous polymer dispersion is substantially free of monoolefinic unsaturated carboxylic acids, and thereby the aqueous emulsion polymerization is optionally carried out in the presence of chain transfer compounds.

Description

[0001] This invention relates to aqueous polymer dispersions that can be obtained by free radical aqueous emulsion polymerization of an olefinically unsaturated monomer M, wherein the olefinically unsaturated monomer M comprises

[0002] a) A combination of the following substances, based on the total weight of monomer M, ranging from 0.5 wt% to 5.0 wt%.

[0003] a1) At least one monomer Ma1, which is selected from C2-C6 (meth)acrylate hydroxyalkyl esters;

[0004] a2) At least one monomer Ma2, selected from mono-olefinic unsaturated monosulfonic acids having 2 to 10 carbon atoms and their salts;

[0005] b1) At least one monomer Mb1, based on 50% to 75.45% by weight of the total weight of monomer M, selected from nonionic monoolefinic unsaturated monomers having a solubility of up to 60 g / L in deionized water at 25 °C and 1 bar, and whose homopolymer has a glass transition temperature Tg of at least 50 °C.

[0006] b2) At least one monomer Mb2, based on 24% to 49.45% by weight of the total weight of monomer M, selected from nonionic monoolefinic unsaturated monomers having a solubility of up to 60 g / L in deionized water at 25 °C and 1 bar, and whose homopolymer has a glass transition temperature Tg of up to 40 °C.

[0007] c) Optional 0.05% to 2.0% by weight of at least one crosslinking monomer Mc;

[0008] Thus, the aqueous polymer dispersion is substantially free of mono-olefinic unsaturated carboxylic acids, and the aqueous emulsion polymerization is optionally carried out in the presence of chain transfer compounds.

[0009] The present invention also relates to a method for producing an aqueous polymer dispersion. This aqueous polymer dispersion can be used as a binder in aqueous coating formulations, particularly as a binder in aqueous coating formulations for molding mineral products. Background Technology

[0010] Polymer dispersions of olefinically unsaturated monomers M are commonly known, particularly as binder components. As binders, especially in coatings, one of the important requirements for such binders is that they provide high mechanical strength and hardness to the coating, and thus good resistance to mechanical shock and good anti-blocking properties. Simultaneously, the coating must be elastic to compensate for mechanical stress. For external coatings (such as architectural coatings and coatings used for molding mineral products), low water absorption and good stain resistance, as well as good resistance to lichen and moss growth, are also desired.

[0011] Molded mineral articles are articles made essentially of mineral materials containing mineral binders, particularly cementitious binders. Specifically, molded articles are products prepared by molding a hydraulic composition (e.g., mortar) comprising a mineral binder, water, aggregates, and (if appropriate) pigments and additives, and subsequently hardening it over time (if appropriate, by exposure to elevated temperatures). Mineral binders are finely broken inorganic substances, such as lime, gypsum, clay, fly ash, volcanic ash, and / or cement, which are hydraulic, meaning they undergo stone-like hardening over time when mixed with water. In mortar, the mineral binder will similarly harden or solidify. Therefore, mortar undergoes stone-like hardening over time, either in air or underwater, and if appropriate, by exposure to elevated temperatures. Molded mineral products, more particularly concrete roofing tiles, may include several layers of mineral material comprising one or more mineral binders, wherein the different layers may have the same or different overall composition (see, for example, DE 3932573 and GB 2,030,890).

[0012] Examples of molded mineral articles for coating according to the invention are concrete pipes for conveying wastewater, concrete roof tiles, curbs, steps, floors, base plates based on mineral binders, and fiber cement flat plates and fiber cement boards, i.e., flat molded mineral articles filled with organic or inorganic fibers (such as, for example, polyester or nylon fibers).

[0013] One specific problem associated with molded mineral products is the occurrence of blooming. These phenomena can be attributed to the fact that mineral binders contain polyvalent cations, such as Ca in an alkaline environment. 2+ When exposed to water, ionic components leach out and migrate to the surface, where they react with carbon dioxide from the air, resulting in unsightly and relatively insoluble white limescale spots on the surface of molded mineral products. Frosting can occur during the actual hardening or curing of newly prepared molded mineral products, during storage in their packaging, or when hardened molded mineral products are exposed to weathering.

[0014] To mitigate the aforementioned problems, molded mineral products are typically coated. For this purpose, waterborne coating compositions whose binder component is a waterborne polymer dispersion are commonly used. Since frosting occurs during the actual setting of the hydraulic composition, this coating is usually applied to the molded mineral product even before it hardens. After curing or setting, a second or more coats can be applied with paint or clear coat materials, followed by drying in each case. However, the properties of first-generation varnishes are not particularly satisfactory in terms of frosting protection. Furthermore, this coating is susceptible to contamination.

[0015] As described in EP 469295, DE 19514266, EP 821660 and DE 10343726, coatings based on styrene / acrylate dispersions or pure acrylate dispersions improve the protection of molded mineral articles against the aforementioned blooming.

[0016] Existing coatings all suffer from the drawback of relatively high water absorption. This high water absorption carries the risk of leaching of low molecular weight components of the coating (such as surfactants often used in the preparation of water-based formulations) during long-term weathering. This high water absorption manifests, for example, as increased whitening or embrittlement of the coating.

[0017] EP 915071 discloses a coating composition for coating molded mineral articles, wherein the coating composition contains an aqueous polymer dispersion as a binder, the aqueous polymer dispersion being based on a copolymer containing more than 0.2% to 5% by weight of an olefinically unsaturated monomer of itaconic acid and having a reduced water absorption rate.

[0018] WO 2009 / 080614 discloses an aqueous polymer dispersion prepared by a gradient feed technique via free radical emulsion polymerization of monomer M comprising an acidic monomer and monomers Mb1 and Mb2, wherein different monomers, particularly the acidic monomer, are fed into the emulsion polymerization reaction at different dosage rates. While the polymer dispersion reduces water absorption, there is still room for improvement.

[0019] WO 2021 / 209543 discloses a further improved adhesive for coatings with unprecedentedly low water absorption.

[0020] However, even coatings optimized to have ultra-low water absorption still tend to turn white or crack when exposed to water in coatings with low pigment volume concentration.

[0021] EP 3896103 describes styrene acrylates containing a large amount of carboxylic acids and sulfonic acids as well as hydroxyl functional monomers for use in textile and nonwoven applications. Summary of the Invention

[0022] The object of this invention is to provide a binder for waterborne coating compositions suitable for external applications, particularly for coating molded mineral products such as concrete roof tiles, paving slabs, and fiber cement coatings. These fiber cement coatings combine low water-induced whitening tendency and crack-free film formation with properties typically desired for such coatings, such as providing frosting protection and maintaining a good visual appearance even after prolonged exposure to moisture and / or sunlight. Furthermore, the binder should be able to be formulated as waterborne paints and varnishes, producing good coating properties such as high mechanical strength, high frosting protection, low whitening tendency, and good resistance to dirt / fouling, resistance to lichen and moss growth, and exhibiting good film-forming properties.

[0023] Surprisingly, the aforementioned problems were solved by aqueous polymer dispersions that can be obtained through the free radical aqueous emulsion polymerization of olefinically unsaturated monomers M, which contain...

[0024] a) A combination of the following substances, based on the total weight of monomer M, ranging from 0.5 wt% to 5.0 wt%.

[0025] a1) At least one monomer Ma1, which is selected from C2-C6 (meth)acrylate hydroxyalkyl esters and their salts;

[0026] a2) At least one monomer Ma2, selected from mono-olefinic unsaturated monosulfonic acids having 2 to 10 carbon atoms and their salts;

[0027] b1) At least one monomer Mb1, based on 50% to 75.45% by weight of the total weight of monomer M, selected from nonionic monoolefinic unsaturated monomers having a solubility of up to 60 g / L in deionized water at 25 °C and 1 bar, and whose homopolymer has a glass transition temperature Tg of at least 50 °C.

[0028] b2) At least one monomer Mb2, based on 24% to 49.45% by weight of the total weight of monomer M, selected from nonionic monoolefinic unsaturated monomers having a solubility of up to 60 g / L in deionized water at 25 °C and 1 bar, and whose homopolymer has a glass transition temperature Tg of up to 40 °C.

[0029] c) Optional 0.05% to 2.0% by weight of at least one crosslinking monomer Mc;

[0030] The aqueous emulsion polymerization is optionally carried out in the presence of a chain transfer compound, and thus the aqueous polymer dispersion is substantially free of mono-olefinic unsaturated carboxylic acids.

[0031] Therefore, a first aspect of the present invention relates to aqueous polymer dispersions that can be obtained by free radical aqueous emulsion polymerization of an olefinically unsaturated monomer M as defined herein, wherein the aqueous emulsion polymerization is preferably carried out in the presence of a chain transfer compound.

[0032] A second aspect of the invention is a method for preparing an aqueous polymer dispersion comprising a free radical aqueous emulsion polymerization of a monomer M as defined herein, wherein the aqueous emulsion polymerization is preferably carried out in the presence of a chain transfer compound.

[0033] Other aspects of the invention relate to the use of aqueous polymer dispersions as defined herein as binders or co-binders in aqueous coating compositions, particularly in architectural coating compositions and in coating compositions for molding mineral articles.

[0034] The present invention also relates to waterborne coating compositions comprising waterborne polymer dispersions as described herein.

[0035] Other aspects of the invention relate to a method for producing a permanent coating on a surface, the method comprising applying an aqueous coating composition according to the invention to the surface and drying the composition to produce a coating.

[0036] The aqueous polymer dispersions described herein offer several benefits, particularly

[0037] - Superior combination of water-induced whitening and cracking resistance compared to existing technologies;

[0038] - Excellent coating lifespan during weathering;

[0039] - The coating has a low water absorption rate, which is at least comparable to that of adhesive-containing coatings according to the prior art;

[0040] - High mechanical strength of the coating;

[0041] - Excellent protection against frosting;

[0042] - Good or even improved resistance to dirt / fouling;

[0043] - Good resistance to lichen and moss growth;

[0044] - Excellent film-forming properties. Detailed Implementation

[0045] Here and throughout this specification, the term "waterborne coating composition" means a liquid waterborne coating composition containing an amount of water sufficient to achieve flowability as a continuous phase.

[0046] The terms “wt.%” and “weight%” are used synonymously here and throughout the instruction manual.

[0047] Throughout this specification, the indefinite article "a" includes both singular and plural forms; that is, the indefinite article relating to a component of the composition indicates whether the component is a single compound or multiple compounds. Unless otherwise stated, the indefinite article "a" is used synonymously with "at least one".

[0048] Here and throughout the specification, the term “pphm” means parts by weight per 100 parts of monomer and corresponds to a relative amount of a certain monomer in weight % based on the total amount of monomer M.

[0049] Throughout this specification, the terms "ethoxylation" and "polyethoxylation" are used synonymously and refer to compounds having oligomeric or polyoxyethylene groups formed by repeating units O-CH2CH2. In this document, the term "degree of ethoxylation" refers to the number average of the repeating units O-CH2CH2 in these compounds.

[0050] Here and throughout the specification, the term “nonionic” in the context of compounds, especially monomers, means that the corresponding compound does not contain any ionic functional groups or any functional groups that can be converted into ionic groups by protonation or deprotonation.

[0051] Throughout this specification, the terms "molded mineral article" and "molded mineral body" are used synonymously. These terms refer to molded articles that are essentially made of mineral materials and contain mineral binders, particularly cementitious binders, as specifically described at the beginning.

[0052] Here and throughout the specification, the term “substantially free” means less than 0.2 pphm, preferably less than 0.1 pphm, and most preferably 0 pphm.

[0053] The prefix C used here and throughout the specification in conjunction with the compound or molecule part n -C m Each indicates a range of possible carbon atoms that a molecule or compound can have. The term "C1-C" n "Alkyl" refers to a group of straight-chain or branched saturated hydrocarbon groups having 1 to n carbon atoms. The term "C"... n / C m "Alkyl" indicates a mixture of two alkyl groups, one with n carbon atoms and the other with m carbon atoms.

[0054] Throughout this specification and in all its contents, the term "olefinic unsaturated monomer" should be understood as a monomer having at least one C=C double bond, such as 1, 2, 3, or 4 C=C double bonds, which is free radical polymerizable, i.e., it polymerizes under aqueous free radical emulsion conditions to obtain a polymer with a carbon-atom backbone. Throughout this specification and in all its contents, the term "monoolefinic unsaturated monomer" should be understood as a monomer having a single C=C double bond, which is readily free radical polymerizable under aqueous free radical emulsion polymerization conditions.

[0055] For example, the term C1-C 20 Alkyl means a group having a straight-chain or branched saturated hydrocarbon group having 1 to 20 carbon atoms, while the term C1-C4 alkyl means a group having a straight-chain or branched saturated hydrocarbon group having 1 to 4 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylpropyl (isopropyl), 1,1-dimethylethyl (tert-butyl), pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl The isomers of C1-C4 alkyl groups, including methyl, ethyl, propyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, isotracene, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, dodecyl, isotracene, dodecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, dodecyl, isotracene, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, dodecyl, and dodecyl, particularly mixtures of isomers, such as "isononyl" and "isodecyl". Examples of C1-C4 alkyl groups are, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, or 1,1-dimethylethyl.

[0056] As used in this article, the term "C5-C" 20 "-Cycloalkyl" refers to a monocyclic or bicyclic alicyclic group that is unsubstituted or substituted with one, two, three, or four C1-C4 alkyl groups (e.g., methyl groups), wherein the C5-C6 group is a cycloalkyl group. 20 -The total number of carbon atoms in cycloalkyl groups is 5 to 20. (C5-C) 20Examples of -alkyl groups include, but are not limited to, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclohexadecyl, norbornyl (= bicyclo[2.2.1]heptyl) and isobornyl (= 1,7,7-trimethylbicyclo[2.2.1]heptyl).

[0057] Term C2-C 10 -alkylene refers to a divalent straight-chain or branched saturated hydrocarbon group (C2-C6-alkylene and C2-C4-alkylene, respectively) having 2 to 10 carbon atoms, particularly 2 to 6 or 2 to 4 carbon atoms, such as ethylenedimethyl, propylenedimethyl, and butadiyl, wherein the group attached to the C2-C4-alkylene preferably does not have a C2-C6 bond. 10 - Alkyl groups are bonded together with the same carbon atom, such as 1,2-ethylenediyl, 1,2-propanediyl, 1,2-butanediyl, 2,3-butanediyl, 2-methyl-1,2-propanediyl, 1,3-propanediyl, 1,4-butanediyl, 1,3-butanediyl, 2-methyl-1,3-propanediyl, 1,5-pentanediyl, 1,5-hexanediyl, etc.

[0058] As used herein, the term "phenylene" refers to a divalent phenyl group, such as 1,2-phenylene and 1,4-phenylene. C1-C4-alkylphenylene indicates phenylene in which the benzene ring is substituted with an alkyl group.

[0059] As used herein, the term "phenyl-C2-C4-alkylene" refers to a C2-C4-alkylene as defined herein, wherein one hydrogen atom is replaced by a phenyl group.

[0060] Throughout this specification and in general, the term "mono-olefinic unsaturated carboxylic acid" refers to mono-olefinic unsaturated monocarboxylic acids having 3 to 6 carbon atoms, such as acrylic acid, methacrylic acid, butenoic acid, 2-ethylacrylic acid, 2-propylacrylic acid, 2-acryloyloxyacetic acid, and 2-methacryloyloxyacetic acid, as well as mono-olefinic unsaturated dicarboxylic acids having 4 to 6 carbon atoms, such as itaconic acid and fumaric acid. Acrylic acid and methacrylic acid are particularly preferred.

[0061] Here and throughout the specification, the term “C2-C6 (meth)acrylate hydroxyalkyl ester” refers to a mono-olefinic unsaturated monocarboxylic acid having 3 to 6 carbon atoms, particularly a hydroxy-C2-C6-alkyl ester of acrylic acid or methacrylic acid, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate or 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate or 3-hydroxypropyl methacrylate and 4-hydroxybutyl methacrylate, hydroxypentyl (meth)acrylate or hydroxyhexyl (meth)acrylate, particularly 2-hydroxyethyl methacrylate.

[0062] According to the present invention, monomer M comprises a combination of at least one monomer Ma1 and at least one monomer Ma2:

[0063] The monomer Ma1 is preferably selected from the group consisting of: Ma1, which is selected from C2-C6 (meth)acrylates and their salts;

[0064] Based on the total amount of monomer M, the total amount of monomer Ma1 is in the range of 0.25 wt% to 2.5 wt%, preferably in the range of 0.35 wt% to 2.0 wt%, and most preferably in the range of 0.5 wt% to 1.5 wt%.

[0065] The monomer Ma2 is selected from the group consisting of: mono-olefinic unsaturated sulfonic acids having 2 to 10 carbon atoms, particularly 2 to 8 carbon atoms, such as vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, and monomers of general formula (I).

[0066] (I)

[0067] in

[0068] X is NH or O.

[0069] R 11 It is hydrogen or methyl.

[0070] R 12 Selected from the group consisting of C2-C6-alkylene, phenylene, phenyl-C1-C2-alkylene, and C1-C2-alkylenephenyl, wherein R 12 Specifically selected from the group consisting of C2-C6-alkylene groups,

[0071] And its salts, preferably its ammonium, sodium, potassium, magnesium and / or calcium salts, especially its sodium or potassium salts. In formula (I), X is preferably NH. In formula (I), R 12 Preferably, it is a C2-C6-alkylene compound, such as 1,2-ethylene, 1,3-propylene, 1,2-propylene, 1-methyl-1,2-propylene, 1,4-butene, 1,3-butene, etc.

[0072] Specifically, the monomer Ma2 is selected from monomers of formula (I) and their salts, preferably their ammonium, sodium, potassium, magnesium, and / or calcium salts, especially their sodium or potassium salts. Examples of monomers of formula (I) include 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methacrylamido-2-methylpropanesulfonic acid, 2-acrylamidobutyric acid, 3-acrylamido-3-methylbutyric acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidobutyric acid, 3-methacrylamido-3-methylbutyric acid, 2-methacrylamido-2,4,4-trimethylpentanesulfonic acid, 2-sulfoethyl acrylate, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, and their salts, especially their ammonium, sodium, potassium, magnesium, and / or calcium salts, especially their sodium or potassium salts.

[0073] In particular, the monomer Ma2 is 2-acryloylamino-2-propanesulfonic acid (AMPS) and / or its salts, especially sodium 2-acryloylamino-2-propanesulfonic acid (AMPS-Na), or a mixture consisting of at least 50% by weight, especially at least 70% by weight, of AMPS and / or at least one salt thereof, based on the total amount of monomer Ma2 and at least another monomer Ma2 as defined herein.

[0074] Based on the total amount of monomer M, the total amount of monomer Ma2, calculated in the form of sulfonic acid, is preferably in the range of 0.25 wt% to 2.55 wt%, particularly 0.35 wt% to 2.0 wt%, especially in the range of 0.5 wt% to 1.5 wt%.

[0075] Based on the total amount of monomer M, the total amount of the combination of monomers Ma1 and Ma2 is in the range of 0.5 wt% to 5.0 wt%, particularly in the range of 0.7 wt% to 4.0 wt%, and especially in the range of 1.0 wt% to 3.0 wt%.

[0076] Preferably, monomer M comprises 0.5% to 5.0% by weight of the following substances based on the total amount of monomer M.

[0077] a1) at least one monomer Ma1, selected from hydroxyethyl methacrylate, in an amount of 0.25% to 2.5% by weight based on the total amount of monomer M;

[0078] a2) At least one monomer Ma2, comprising or being 2-acrylamidopropyl-2-methylpropanesulfonic acid or a salt thereof, in 0.25% to 2.5% by weight based on the total amount of monomer M and calculated in sulfonic acid form.

[0079] Monomer M further comprises at least monomer Mb1 as defined above, which is nonionic and slightly soluble in water, i.e., its solubility in deionized water at 25°C and 1 bar is at most 60 g / L, for example in the range of 0.1 g / L to 60 g / L, and is characterized in that its homopolymer has a glass transition temperature Tg of at least 50°C, particularly in the range of 55°C to 200°C, particularly in the range of 60°C to 180°C.

[0080] Based on the total amount of monomer M, the total amount of monomer Mb1 is preferably in the range of 50% to 75.45% by weight, and more preferably 55% to 64.45% by weight.

[0081] Monomer M further comprises at least monomer Mb2 as defined above, which is nonionic and slightly soluble in water, i.e., its solubility in deionized water at 25°C and 1 bar is at most 60 g / L, for example in the range of 0.1 g / L to 60 g / L, and is characterized in that the glass transition temperature Tg of its homopolymer is at most 40°C, particularly in the range of -80°C to +40°C.

[0082] Based on the total amount of monomer M, the total amount of monomer Mb2 is preferably in the range of 24 wt% to 49.45 wt%, and more preferably 35 wt% to 44.45 wt%.

[0083] The actual Tg values ​​of the homopolymers of monomers Mb1 and Mb2 are known and are listed, for example, in Ullmann's Encyclopädie der technischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], 5th edition, Volume A21, page 169, Verlag Chemie, Weinheim, 1992. Other sources of glass transition temperatures for homopolymers are, for example, J. Brandrup, EH Immergut, Polymer Handbook, 1st edition, J. Wiley, New York, 1966; 2nd edition, J. Wiley, New York, 1975; 3rd edition, J. Wiley, New York, 1989; and 4th edition, J. Wiley, New York, 2004. These glass transition temperatures can also be experimentally determined according to ISO 11357-2:2013 by differential scanning calorimetry (DSC), preferably with sample preparation according to ISO 16805:2003.

[0084] Suitable monomer Mb1 is a monovinyl aromatic monomer, such as styrene, C1-C2-alkyl esters of methacrylate, such as methyl methacrylate and ethyl methacrylate, tert-butyl methacrylate, tert-butyl acrylate, and mixtures thereof. Specifically, monomer Mb1 comprises at least one of C1-C2-alkyl esters of methacrylate and tert-butyl acrylate. Specifically, monomer Mb1 comprises methyl methacrylate. Specifically, based on the total amount of monomer Mb1, monomer Mb1 is selected from the group consisting of methyl methacrylate and combinations thereof with tert-butyl acrylate.

[0085] The suitable monomer Mb2 is the C1-C of acrylic acid. 20 -Alkyl esters (excluding tert-butyl acrylate), C5-C of acrylic acid 20 -Cycloalkyl esters, C3-alkyl esters of methacrylate, n-butyl methacrylate, C5-C esters of methacrylate 20 -Alkyl esters, C8-C of methacrylic acid 20 - Cycloalkyl esters and mixtures thereof.

[0086] Suitable C1-C of acrylic acid 20 -Alkyl esters include, but are not limited to, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, isodecyl acrylate, 2-propylheptyl acrylate, lauryl acrylate, and C-acrylate. 12 / C 14 -Alkyl ester, C-acrylate 12 -C 15 -Alkyl ester, isotridecyl acrylate, C-acrylate 16 / C 18 -Alkyl esters and stearyl acrylates.

[0087] Suitable acrylic C5-C 20 -Cycloalkyl esters include, but are not limited to, cyclohexyl acrylate, norbornyl acrylate, and isobornyl acrylate.

[0088] Suitable C3-alkyl esters of methacrylic acid and C5-C esters of methacrylic acid 20 -Alkyl esters include, but are not limited to, n-propyl methacrylate, isopropyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, n-decyl methacrylate, 2-propylheptyl methacrylate, lauryl methacrylate, and C-methacrylate. 12 / C 14 -Alkyl ester, C-methacrylic acid 12 -C 15-Alkyl ester, isotridecyl methacrylate, C-methacrylate 16 / C 18 -Alkyl esters and stearyl methacrylate.

[0089] Suitable C5-C of methacrylic acid 16 -Cycloalkyl esters include, but are not limited to, cyclohexyl methacrylate, norbornyl methacrylate, and isobornyl methacrylate.

[0090] Preferably, the monomer Mb2 is the C2-C of acrylic acid. 10 Alkyl esters (excluding tert-butyl acrylate) and n-butyl methacrylate, wherein the C2-C of acrylic acid 10 -Alkyl esters are specifically selected from the group consisting of: ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate and mixtures thereof, such as mixtures of n-butyl acrylate and 2-ethylhexyl acrylate, mixtures of n-butyl acrylate and ethyl acrylate, mixtures of n-butyl acrylate and n-butyl methacrylate, mixtures of n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate, and mixtures of ethyl acrylate, n-butyl acrylate, n-butyl methacrylate and 2-ethylhexyl acrylate.

[0091] Monomer M also comprises at least one crosslinking monomer Mc. Suitable crosslinking monomers are olefinic unsaturated monomers having at least one functional group capable of reacting with itself or with other functional groups within the polymer formed by the polymerization of monomer M (hereinafter referred to as monomer Mc1). Suitable crosslinking monomers are particularly polyolefinic unsaturated monomers having at least two, particularly two to six, non-conjugated olefinic unsaturated double bonds, hereinafter referred to as monomer Mc2. Suitable monomers are also monoolefinic unsaturated monomers having at least one other functional group capable of reacting with itself or with a carboxylic acid group (hereinafter also referred to as monomer Mc2), and mixtures of different monomers Mc. Monomer Mc can also be a combination of two or more different monomers Mc, for example, a combination of at least one monomer Mc1 and at least one monomer Mc2.

[0092] Based on the total amount of monomer M, the total amount of monomer Mc is preferably in the range of 0.05 wt% to 1.5 wt%, especially in the range of 0.08 wt% to 1.0 wt%.

[0093] The reactive group of monomer Mc1 can be, for example, an ethylene oxide group, such as a glycidyl group, or a silyl group having at least one Si-bonded alkoxy group, including, for example, alkyldialkoxysilyl groups such as methyldimethoxysilyl, ethyldimethoxysilyl, methyldiethoxysilyl, and ethyldiethoxysilyl, and trialkoxysilyl groups such as trimethoxysilyl and triethoxysilyl. In the context of silyl groups, the term alkyl specifically refers to an alkyl group having 1 to 4 carbon atoms. The term alkoxy refers to an alkoxy group having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, and butoxy.

[0094] Examples of the monomer Mc1 include, but are not limited to,

[0095] - Glycidyl esters of monoalkenyl unsaturated monocarboxylic acids having 3 to 6 carbon atoms, hereinafter referred to as monomers Mc1.1, particularly glycidyl acrylate and glycidyl methacrylate;

[0096] - Monoolefinic unsaturated monomers having at least one trialkoxysilyl group or at least one alkyldialkoxysilyl group, hereinafter referred to as monomers Mc1.2. Examples of these monomers Mc1.2 include vinyltrialkoxysilanes, such as vinyltrimethoxysilane, and alkylvinyldialkoxysilanes, such as methylvinyldialkoxysilane. Examples of these monomers Mc1.2 also include alkyl diekoxysilyl alkyl esters of monoalkenyl unsaturated monocarboxylic acids having 3 to 6 carbon atoms, particularly alkyl diekoxysilyl alkyl esters of acrylic acid and alkyl diekoxysilyl alkyl esters of methacrylic acid, such as (meth)acryloyloxypropyl-methyldimethoxysilane and (meth)acryloyloxypropyl-methyldiethoxysilane, and trialkoxysilyl alkyl esters of monoalkenyl unsaturated monocarboxylic acids having 3 to 6 carbon atoms, particularly trialkoxysilyl alkyl esters of acrylic acid and trialkoxysilyl alkyl esters of methacrylic acid, such as (meth)acryloyloxypropyl-trimethoxysilane and (meth)acryloyloxypropyl-triethoxysilane, and mixtures thereof.

[0097] Among the monomers Mc1, preferred are the monomers Mc1.2 and combinations of at least one monomer Mc1.2 with one or more monomers Mc1.1.

[0098] In the monomer Mc1.2, preferred are trialkoxysilyl alkyl esters of monoalkenyl unsaturated monocarboxylic acids having 3 to 6 carbon atoms, particularly trialkoxysilyl alkyl esters of acrylic acid and trialkoxysilyl alkyl esters of methacrylic acid, such as (meth)acryloyloxypropyl-trimethoxysilane and (meth)acryloyloxypropyl-triethoxysilane and mixtures thereof.

[0099] Examples of suitable monomeric Mc2 include

[0100] - Polyacrylates, polymethacrylates, polyallyl ethers, or polyvinyl ethers of polyols having at least two OH groups, such as two to six OH groups, are hereinafter referred to as monomer Mc2.1. The OH groups of the polyols may be fully or partially etherified or esterified, provided that they have an average of at least two, such as two to six, olefinic unsaturated double bonds. Examples of polyol components in such crosslinking agents Mc2.1 include, but are not limited to, diols such as 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, but-2-en-1,4-diol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, neopentanediol, 3-methylpentane-1,5-diol, 2,5-dimethyl-1,3-hexanediol, 2,2 4-Trimethyl-1,3-pentanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-bis(hydroxymethyl)cyclohexane, neopentanediol monoester of hydroxyneopentanoate, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis[4-(2-hydroxypropyl)phenyl]propane, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 3-thiapentane-1,5-diol, and block copolymers of polyethylene glycol, polypropylene glycol, ethylene oxide or propylene oxide, random copolymers of ethylene oxide and propylene oxide, and polytetrahydrofuran with a molecular weight of 200 to 10,000 in each case. Examples of polyols having more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, cyanuric acid, sorbitol, and sugars (such as sucrose, glucose, and mannose). The polyol component in this type of crosslinking agent Mc2.1, having more than two OH groups, can be alkoxylated with ethylene oxide or propylene oxide.

[0101] - Monoesters of monoalkenyl unsaturated C3-C6 monocarboxylic acids, particularly acrylic acid or methacrylic acid, with monoalkenyl unsaturated aliphatic or alicyclic monohydroxy compounds, hereinafter referred to as monomers Mc2.2. Examples include vinyl acrylate, vinyl methacrylate, allyl acrylate, allyl methacrylate, cyclohexyl-2-enyl acrylate, cyclohexyl-2-enyl methacrylate, norbornyl acrylate, and norbornyl methacrylate;

[0102] - A straight-chain or branched, linear or cyclic aliphatic or aromatic hydrocarbon having at least two double bonds, which, in the case of aliphatic hydrocarbons, must not be conjugated, hereinafter referred to as monomer Mc2.3. Examples include divinylbenzene, divinyltoluene, 1,7-octadiene, 1,9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane, or polybutadiene with a molecular weight of 200 to 20,000, particularly divinyl aromatic compounds such as 1,3-divinylbenzene and 1,4-divinylbenzene.

[0103] Among the monomers Mc2, the preferred monomers are Mc2.2, especially acrylates and methacrylates, particularly allyl acrylate and allyl methacrylate.

[0104] In a particular set of embodiments, the monomer Mc comprises at least one monomer Mc1.2, which is particularly selected from the group consisting of: monoalkenyl unsaturated monomers having at least one trimekryl group, particularly trimekryl alkyl esters of monoalkenyl unsaturated monocarboxylic acids having 3 to 6 carbon atoms, and more particularly selected from the group consisting of: trimekryl alkyl esters of acrylic acid and trimekryl alkyl esters of methacrylic acid, such as (meth)acryloyloxypropyl-trimethoxysilane and (meth)acryloyloxypropyl-triethoxysilane and mixtures thereof.

[0105] In this particular set of embodiments, monomer Mc1.2 may be the only monomer Mc. In this particular set of embodiments, monomer Mc may also be a combination of at least one monomer Mc1.2 and at least one monomer Mc that is different from monomer Mc1.2 (e.g., monomer Mc1.1 or monomer Mc2, particularly monomer Mc2.2). Among the combinations of at least one monomer Mc1.2 and at least one monomer Mc that is different from monomer Mc1.2, a combination of at least one monomer Mc1.2 with at least one monomer Mc1.1 preferably selected from glycidyl acrylate and glycidyl methacrylate, and a combination of at least one monomer Mc1.2 with at least one monomer Mc2.2 preferably selected from allyl acrylate and allyl methacrylate, are particularly preferred.

[0106] In a set of preferred embodiments, monomer M comprises

[0107] a) A combination of monomers comprising 0.5% to 5.0% by weight of monomer M in total, wherein the monomers contain

[0108] a1) at least one monomer Ma1, selected from hydroxyethyl methacrylate, in an amount of 0.25% to 2.5% by weight based on the total amount of monomer M;

[0109] a2) 0.25% to 2.5% by weight of at least one monomer Ma2, calculated in sulfonic acid form based on the total amount of monomer M, comprising or being 2-acrylamidopropyl-2-methylpropanesulfonic acid or a salt thereof.

[0110] b1) at least one monomer Mb1, particularly at least one preferred monomer Mb1, in 50% to 75.45% by weight of the total amount of monomer M;

[0111] b2) At least one monomer Mb2, selected from the C2-C group of acrylic acid, comprising 24% to 49.45% by weight of the total amount of monomer M. 10 -Alkyl esters and n-butyl methacrylate, wherein the C2-C of acrylic acid 10 -Alkyl esters are specifically selected from the group consisting of: ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, 2-propylheptyl acrylate and mixtures thereof, such as mixtures of n-butyl acrylate and 2-ethylhexyl acrylate, mixtures of n-butyl acrylate and ethyl acrylate, mixtures of n-butyl acrylate and n-butyl methacrylate, mixtures of n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate, and mixtures of ethyl acrylate, n-butyl acrylate, n-butyl methacrylate and 2-ethylhexyl acrylate;

[0112] c) 0.05% to 2.0% by weight of at least one monomer Mc, particularly at least one preferred monomer Mc, more preferably at least one monomer Mc1.2 or a combination of at least one monomer Mc1.2 with at least one monomer Mc1.1 and / or at least one monomer Mc2.2, based on the total amount of monomer M.

[0113] In embodiments of the foregoing group, monomer Mc1.2 is preferably selected from the group consisting of: trimekryl alkyl esters of acrylic acid and trimekryl alkyl esters of methacrylic acid, such as (meth)acryloyloxypropyl-trimethoxysilane and (meth)acryloyloxypropyl-triethoxysilane and mixtures thereof.

[0114] In the embodiments of the aforementioned group, monomer Mc1.1 is preferably selected from the group consisting of glycidyl acrylate and glycidyl methacrylate.

[0115] In embodiments of the aforementioned group, monomer Mc2.2 is preferably selected from the group consisting of: vinyl acrylate, vinyl methacrylate, allyl acrylate, allyl methacrylate, cyclohexyl-2-enyl acrylate, cyclohexyl-2-enyl methacrylate, norbornel acrylate and norbornel methacrylate, and particularly from the group consisting of allyl acrylate and allyl methacrylate.

[0116] Typically, the total weight of monomers Ma1, Ma2, Mb1, Mb2, and Mc is at least 95% by weight, particularly at least 98% by weight, especially at least 99% by weight, or 100% by weight of the total amount of monomer M. Those skilled in the art will immediately understand that the figures given for the weights of monomers Ma1, Ma2, Mb1, Mb2, and Mc will not exceed 100% by weight.

[0117] Optionally, monomer M further comprises at least one nonionic monoolefinic unsaturated monomer Md, which is different from the aforementioned monomers Mb1, Mb2 and Mc, and preferably has a functional group selected from carboxamide groups, urea groups and ketone groups.

[0118] An example of a monomer Md having a carboxamide group is

[0119] - Primary amides of monoalkenyl unsaturated monocarboxylic acids having 3 to 6 carbon atoms, such as acrylamide and methacrylamide;

[0120] -N-C1-C monoalkenyl unsaturated monocarboxylic acids with 3 to 6 carbon atoms 10 Alkylamides, especially N-C1-C of acrylic acid or methacrylic acid 10 Alkylamides, such as N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-isopropylacrylamide, N-butylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-propylmethacrylamide, N-isopropylmethacrylamide, and N-butylmethacrylamide.

[0121] Examples of monomers Md having a urea group are 2-(2-oxo-imidazolium-1-yl)ethyl acrylate, 2-(2-oxo-imidazolium-1-yl)ethyl methacrylate (also known as 2-ureoyl(meth)acrylate), N-(2-acryloyloxyethyl)urea, N-(2-methacryloyloxyethyl)urea, N-(2-(2-oxo-imidazolium-1-yl)ethyl)acrylamide, N-(2-(2-oxo-imidazolium-1-yl)ethyl)methacrylamide, 1-allyl-2-oxoimidazoline, and N-vinylurea.

[0122] Examples of monomers Md having a ketone group are acetylacetoxyethyl acrylate, acetylacetoxypropyl methacrylate, acetylacetoxybutyl methacrylate, 2-(acetylacetoxy)ethyl methacrylate, diacetone acrylamide (DAAM), diacetone acrylamide, and diacetone methacrylamide.

[0123] Typically, based on the total amount of monomer M, the amount of monomer Md will not exceed 5% by weight, particularly 3% by weight, and especially 2% by weight. In particular, monomer M does not contain monomers other than monomers Ma1, Ma2, Mb1, Mb2 and Mc.

[0124] According to the present invention, an aqueous polymer dispersion is prepared in the presence of at least one chain transfer compound.

[0125] Generally, chain transfer compounds are understood to be compounds that transfer free radicals, thereby stopping or controlling polymer chain growth during polymerization and thus reducing the molecular weight of the resulting polymer. Typically, chain transfer compounds have at least one readily abstractable hydrogen atom. Preferably, the abstractable hydrogen is part of a thiol group (i.e., the SH group), also known as a "thiol group".

[0126] Chain transfer compounds are specifically selected from the group consisting of:

[0127] -SH-substituted C2-C6 alkyl acids (hereinafter referred to as C2-C6 thioalkyl acids) C1-C 20 -Alkyl esters (chain transfer compounds T.1), especially the C1-C of mercaptoacetic acid (=thioglycolic acid) 20 -alkyl esters, such as methyl mercaptoacetate, ethyl mercaptoacetate, n-butyl mercaptoacetate, n-hexyl mercaptoacetate, n-octyl mercaptoacetate, 2-ethylhexyl mercaptoacetate, and n-decyl mercaptoacetate, as well as C1-C of mercaptopropionic acid. 20 -alkyl esters, such as methyl mercaptopropionate, ethyl mercaptopropionate, n-butyl mercaptopropionate, n-hexyl mercaptopropionate, n-octyl mercaptopropionate, 2-ethylhexyl mercaptopropionate and n-decyl mercaptopropionate.

[0128] -C1-C 20 -Alkyl thiols (chain transfer compound T.2), especially C6-C 16-alkyl thiols, such as ethanethiol, n-propanethiol, 2-propanethiol, n-butanethiol, 2-butanethiol, 2-methyl-2-propanethiol, n-pentanethiol, 2-pentanethiol, 3-pentanethiol, 2-methyl-2-butanethiol, 3-methyl-2-butanethiol, n-hexanethiol, 2-hexanethiol, 3-hexanethiol, 2-methyl-2-pentanethiol, 3-methyl-2-pentanethiol, 4-methyl-2-pentanethiol, 2-methyl-3-pentanethiol, 3-methyl-3-pentanethiol, 2-ethylbutanethiol, 2-ethyl-2-butanethiol, n-heptanethiol and its isomers, n-octanethiol and its isomers, n-nonanethiol and its isomers, n-decanethiol and its isomers, n-undecanethiol and its isomers, n-dodecanethiol and its isomers such as tert-dodecanethiol, n-tridecanethiol and its isomers;

[0129] -OH-substituted C2-C 20 -alkyl thiols (chain transfer compounds T.3), such as 2-hydroxyethylthiol and 2-hydroxypropanethiol;

[0130] -Aromatic thiols (chain transfer compounds T.4), such as thiophenol, o-methylthiophenol, m-methylthiophenol or p-methylthiophenol;

[0131] - and their mixtures.

[0132] Examples of other chain transfer compounds that can replace or be used in combination with chain transfer compounds T.1 to T.4 are aliphatic and / or aryliphatic halogen compounds, such as n-butyl chloride, n-butyl bromide, n-butyl iodide, dichloromethane, dichloroethane, chloroform, bromoform, bromotrichloromethane, dibromodichloromethane, carbon tetrachloride, carbon tetrabromide, benzyl chloride, benzyl bromide, and aliphatic and / or aromatic aldehydes, such as acetaldehyde, propionaldehyde, and / or benzaldehyde, hydrocarbons having readily abstractable hydrogen atoms, such as toluene, and thiols other than T.1 to T.4, such as the thiols described in Polymer Handbook, 3rd edition, 1989, J. Brandrup and E.H.M.G., John Wiley & Sons, Part II, pages 133-141.

[0133] Particularly preferred are chain transfer compounds T.1 and T2, especially the C4-C4 chain of SH-substituted C2-C4 alkyl acids. 16 -alkyl esters, especially C4-C of mercaptoacetic acid 16 -Alkyl esters, C4-C of mercaptopropionic acid 16 -Alkyl ester, C6-C 16 - Alkyl thiols and mixtures thereof.

[0134] The amount of chain transfer compound, based on the total weight of monomer M, is preferably in the range of 0.05 wt% to 1.2 wt%, particularly in the range of 0.1 wt% to 0.9 wt%, and especially in the range of 0.15 wt% to 0.6 wt%.

[0135] The monomers M that form the polymer can be of petrochemical origin or of biorenewable origin. If they are of biorenewable origin, then in particular, at least 30% by weight of monomer M, preferably at least 40% by weight or at least 50% by weight of monomer M is based on biorenewable origin, which means that their biocarbon content is at least 30 mol% based on the total carbon content in the monomers from biorenewable origin, and particularly at least 40 mol%.

[0136] The term "biocarbon" indicates that the carbon is of biological origin and comes from biomaterials / renewable resources. The content of biocarbon and the content of biomaterials are expressions representing the same value. Renewable-source materials or biomaterials are organic materials in which the carbon originates from CO2 recently (on a human timescale) fixed from the atmosphere through photosynthesis. Biomaterials (100% naturally derived carbon) have a carbon content greater than 10... -12 Typically about 1.2 × 10 −12 of 14 C / 12 C isotope ratios, while fossil materials have a ratio of zero. In fact, isotopes... 14 Carbon is formed in the atmosphere and subsequently integrated through photosynthesis, a process that takes at most a few decades. 14 The half-life of carbon is 5,730 years. Therefore, materials derived from photosynthesis, typically plants, must have the highest content of this isotope. 14 C. The determination of the content of biological materials or biocarbon can be performed according to standard ASTM D6866-12, method B (ASTM D 6866-06) and ASTM D 7026 (ASTM D 7026-04).

[0137] The term "biorenewable source" refers to organic materials in which carbon originates from non-fossil biological sources. Examples of biorenewable sources include, but are not limited to, sugars such as glucose or sucrose; and starch obtained from plants such as corn, cereals, sugarcane, sugar beets, potatoes, sweet potatoes, or cassava; other polysaccharides of plant origin, such as cellulose, lignocellulose, hemicellulose, pectin, chitin, fructan, and pullulan; vegetable oils; and biomass obtained from plants or agricultural waste.

[0138] Monomers and monomer precursors, such as alcohols and fatty acids, can be produced directly from such biological resources via biological processes, including fermentation.

[0139] Examples of monomers and monomer precursors that can be obtained directly from biorenewable sources are alkyl and cycloalkyl esters of acrylic acid, methacrylic acid, itaconic acid, and acrylic acid and methacrylic acid, wherein at least the carbon atoms of the alkyl and cycloalkyl groups are of biological origin, i.e., they are at least partially composed of biocarbon. Specifically, the corresponding alkanols and cycloalkanols used to prepare the alkyl and cycloalkyl esters of acrylic acid and methacrylic acid, respectively, preferably have a biocarbon content of at least 70 mol% based on the total amount of carbon atoms in the respective monomer. This content is advantageously higher, particularly greater than or equal to 80 mol%, preferably greater than or equal to 90 mol%, and advantageously equal to 100 mol%. Similarly, itaconic acid, citraconic acid, and mesoaconic acid can be produced on a large scale from renewable materials, for example, by fermentation of raw materials containing glucose, sucrose, starch, or cellulose. Similarly, acrylic acid and methacrylic acid can be produced from biorenewable sources. Another example is vinyl esters of alkanic acids, wherein at least the alkanic acids are produced from biorenewable sources.

[0140] It is also possible to produce isotope-rich products through the so-called biomass balance method. 14 Monomers of C. Here, biomass or organic waste of natural origin (e.g., agricultural waste) is converted into methane or unsaturated hydrocarbons (naphtha) via fermentation or non-biological classical chemical processes. The resulting methane and / or unsaturated hydrocarbons are optionally combined with petrochemical-derived methane and / or unsaturated hydrocarbons and converted into a monomer with a value greater than zero, for example, >5 × 10⁻⁶. -14 isotope ratio 14 C / 12 C monomers or monomer precursors.

[0141] Generally speaking, the glass transition temperature T of the polymer in the aqueous polymer dispersion of the present invention formed from the polymerized monomer M is... g The glass transition temperature is within the range of 25°C to 70°C, particularly within the range of 28°C to 50°C, and especially within the range of 30°C to 45°C. In the case of multi-level polymers containing two or more polymers or polymer phases each with different glass transition temperatures, the glass transition temperatures of the individual polymer phases may be outside the ranges given here. However, the weight-average glass transition temperature Tg g (av), as calculated by the following equation

[0142] T g (av) = (T g (1)*w1 + Tg(2)*w2 … Tg(n)*w n )

[0143] Within the range of 25°C to 70°C, especially within the range of 28°C to 50°C, and particularly within the range of 30°C to 45°C. In equation T... g In (1), Tg (2) to T g (n) represents the glass transition temperatures of each polymer 1, 2 to n in °C or K, while w1, w2 to w n This represents the amount of each polymer 1, 2 to n in weight % (%).

[0144] The actual glass transition temperature depends on the composition of the monomers M that form the polymer dispersion, specifically on the type and relative amounts of monomers Ma1, Ma2, Ma2, Mb1, Mb2, Mc, and optionally, Md (if present). The theoretical glass transition temperature can be calculated from the composition of the monomers M used in emulsion polymerization. The theoretical glass transition temperature is typically calculated from the monomer composition using the Fox equation:

[0145] 1 / Tg(F) = x1 / Tg1 + x2 / Tg2 + … x n / Tg n .

[0146] In this equation, x1, x2, ..., x n These are the mass fractions of different monomers 1, 2, ..., n, and Tg1, Tg1, ..., Tg n Tg(F) is the glass transition temperature in Kelvin of a homopolymer synthesized from only one of monomers 1, 2, ..., n. Tg(F) is the theoretical glass transition temperature according to Fox's equation. Fox's equation is described by TG Fox in Bull. Am. Phys. Soc. 1956, 1, p. 123, and also in Ullmann's Encyclopädie dertechnischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], Vol. 19, p. 18, 4th edition, Verlag Chemie, Weinheim, 1980. The actual Tg values ​​for homopolymers of most monomers are known and are listed in the references cited above.

[0147] Typically, the theoretical glass transition temperature Tg is calculated using Fox as described in this paper. t The glass transition temperatures are similar to or even the same as those experimentally determined as described in this article, and the deviations from each other do not exceed 5K, and in particular, the deviations do not exceed 2K. Therefore, by selecting appropriate monomers M1, M2…M… n and their mass fractions in the monomer composition, x1, x2, ..., x3 nThe actual and theoretical glass transition temperatures of the polymer are adjusted to achieve the desired glass transition temperatures Tg(1) and Tg(2), respectively. For technicians, selecting appropriate amounts of monomers M1, M2…M… n It is known to obtain copolymers and / or copolymer phases with desired glass transition temperatures. Therefore, monomer M is selected such that a theoretical glass transition temperature Tg(F) according to Fox is achieved, which is in the range of 25°C to 70°C, particularly in the range of 28°C to 50°C, and especially in the range of 30°C to 45°C.

[0148] For the purposes of this invention, it has been found that it is advantageous if the polymer particles contained in the polymer latex have a Z-average particle size in the range of 80 nm to 500 nm, particularly in the range of 80 nm to 300 nm, as determined by quasi-elastic light scattering.

[0149] 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. It can be determined using a high-performance particle size analyzer (HPPS). For this purpose, a sample of aqueous polymer latex is diluted, and the dilution is analyzed. In the case of QELS, the aqueous dilution can have a polymer concentration ranging from 0.001 wt% to 0.5 wt%, depending on the particle size. In most cases, a suitable concentration is 0.01 wt%. However, higher or lower concentrations can be used to obtain the optimal signal-to-noise ratio. Measurement configuration: HPPS from Malvern, automated, equipped with continuous flow cuvettes and a Gilson autosampler. Parameters: Measurement temperature 20.0℃; Measurement time 120 seconds (6 cycles, 20 seconds each); Scattering angle 173°; Laser wavelength 633nm (HeNe); Refractive index of the medium 1.332 (aqueous); Viscosity 0.9546 mPa·s. This measurement yields the average value (fitted average value) of the second-order cumulant analysis, i.e., the Z-mean value. The "fitted average value" is the average intensity-weighted hydrodynamic particle size in nm.

[0150] Hydrodynamic particle size can also be determined by hydrodynamic chromatography (HDC), as described, for example, by H. Wiese, “Characterization of Aqueous Polymer Dispersions”, Polymer Dispersions and Their Industrial Applications (Wiley-VCH, 2002), pp. 41–73. For further details, see the examples and descriptions below.

[0151] The particle size distribution of polymer particles contained in a polymer dispersion is particularly unimodal or nearly unimodal, meaning that the particle size distribution function has a single maximum value. However, the particle size distribution of copolymer particles contained in a polymer latex can also be multimodal, particularly bimodal, meaning that the particle size distribution function has at least two maximum values. Preferably, the first maximum value is in the range of 50 nm to 180 nm and the second maximum value is in the range of 200 nm to 400 nm.

[0152] Preferably, the final polymer dispersion has a pH of at least 7, for example, in the pH range of 7 to 12, before being used in the coating composition.

[0153] The aqueous polymer dispersions of the present invention typically have a solids content in the range of 30% to 75% by weight, preferably in the range of 40% to 65% by weight, and particularly in the range of 45% to 60% by weight.

[0154] Polymer dispersions can be shaped using film-forming auxiliary agents (also known as filming auxiliary agents). It is well known that film-forming auxiliary agents lower the minimum film-forming temperature (MFFT) of a polymer dispersion. The minimum film-forming temperature (MFFT) is the lowest temperature at which polymer particles in a polymer dispersion agglomerate and form a binder film. MFFT is typically determined by applying the polymer dispersion as a thin film to a metal plate with a defined temperature gradient – ​​see DIN ISO 2115: 2001-04.

[0155] Therefore, one aspect of the present invention relates to polymer dispersions as described herein, which contain at least one film-forming aid.

[0156] The amount of film-forming aid is typically chosen such that an MFFT is generated in the range of 0°C to 15°C. Preferably, the amount of film-forming aid is in the range of 2% to 25% by weight, particularly 5% to 20% by weight, based on the total amount of polymer formed from the polymerized monomer M.

[0157] Suitable film-forming aids are solvents, also known as non-permanent plasticizers and permanent plasticizers. Permanent plasticizers typically have lower water solubility and lower volatility than non-permanent plasticizers. In contrast to permanent plasticizers, non-permanent plasticizers will evaporate from the coating and are primarily used for better coalescence of binder particles at low temperatures. Suitable film-forming aids that provide non-permanent plasticization include, for example...

[0158] i) Hydrocarbons, such as white oil and pine oil,

[0159] ii) C2-C4-alkyldiols, also known as C2-C4-alkylene glycols, di-C2-C4-alkylene glycols, tri-C2-C4-alkylene glycols and their mono-C1-C6-alkyl ethers, such as propylene glycol, ethylene glycol, butanediol, diethylene glycol, dipropylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monopropyl ether, dipropylene glycol methyl ether, dipropylene glycol n-butyl ether, propylene glycol tert-butyl ether, tripropylene glycol methyl ether, butyl diethylene glycol (=2-(2-(butoxy)ethoxy)ethanol) and 1-methoxy-2-propanol;

[0160] iii) Monoesters and diesters of C2-C8-alkyldiols, di-C2-C4-alkylenediols and tri-C2-C4-alkylenediols with C2-C4-alkyl acids (such as acetic acid, propionic acid, butyric acid and isobutyric acid), and mono-C1-C6-alkyl ethers of C2-C4-alkyldiols, di-C2-C4-alkylenediols and tri-C2-C4-alkylenediols with monoesters of C2-C4-alkyldiols and C2-C4-alkyl acids, such as butyl glycol acetate, butyl glycol diacetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate and 2,2,2-trimethyl-1,3-pentanediol monoisobutyrate (Texanol). ® );

[0161] iv) Di-C1-C6-alkyl esters of aliphatic dicarboxylic acids having 4 to 8 carbon atoms, such as dibutyl adipate, diisobutyl adipate, diisobutyl succinate, diisobutyl glutarate and diisobutyl maleate.

[0162] v) Diol ethers and diol esters, such as Solvenon ® and Lusolvan ® and Loxanol ® The name was purchased from BASF SE and is named Dowanol. ® The product name was obtained from Dow.

[0163] Suitable external plasticizers with low volatility include the following: dimethyl phthalate, dibutyl phthalate, dioctyl phthalate and other esters of phthalic acid, propoxylated m-cresol with a number-average propoxylation degree of 6, propoxylated p-cresol with a number-average propoxylation degree of 6 and mixtures of these two oligomeric (propylene glycol) cresol ethers, oligomeric (propylene glycol) cresol ethers with a number-average propoxylation degree of 3, oligomeric (propylene glycol) cresol ethers with a number-average propoxylation degree of 12, and oligomeric (propylene glycol) phenyl ethers and oligomeric (propylene glycol) alkylphenyl ethers with a number-average propoxylation degree of 3 to 12, aromatic glycol ethers, ethyl p-toluenesulfonate, alkyl esters of aromatic sulfonic acids, tributoxyethyl phosphate, tri-n-butyl phosphate and other phosphate esters.

[0164] Film-forming aids that are different from hydrocarbons are preferred. Non-permanent plasticizers are also preferred. Film-forming aids from groups ii) to v) are particularly preferred.

[0165] Aqueous polymer dispersions can be prepared by free radical aqueous emulsion polymerization of monomer M. According to the invention, the aqueous emulsion polymerization is preferably carried out in the presence of chain transfer compounds as disclosed herein.

[0166] As previously mentioned, chain transfer compounds having a thiol group are preferred, particularly chain transfer compounds of group T.1 to T.4 above. Chain transfer compounds T.1 and T2 are especially preferred, particularly those of SH-substituted C2-C4 alkyl groups. 16 -alkyl esters, especially C4-C of mercaptoacetic acid 16 -Alkyl esters, C4-C of mercaptopropionic acid 16 -Alkyl ester, C6-C 16 - Alkyl thiols and mixtures thereof.

[0167] The amount of chain transfer compound, based on the total weight of monomer M, is preferably in the range of 0.05 wt% to 1.2 wt%, particularly in the range of 0.1 wt% to 0.9 wt%, and especially in the range of 0.15 wt% to 0.6 wt%.

[0168] Free radical aqueous emulsion polymerization can be carried out as free radical aqueous multi-step emulsion polymerization. Free radical aqueous multi-step emulsion polymerization is a free radical aqueous emulsion polymerization carried out in at least two consecutive polymerization steps, wherein in each step, a portion M' of monomer M is polymerized in the free radical emulsion polymerization, wherein the second polymerization step and any additional polymerization steps are carried out in the polymer dispersion obtained in the previous step.

[0169] Free radical-initiated aqueous emulsion polymerization 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, such as hydrogen peroxide or persulfate, monoalkali metal salts or dialkali metal salts or ammonium salts such as monosodium salts, monopotassium salts or monoammonium salts and disodium salts, dipotassium salts or diammonium salts, or organic peroxides, such as alkyl hydroperoxides, such as tert-butyl hydroperoxide, p-menthyl hydroperoxide or cumyl hydroperoxide, and dialkyl peroxides or diaryl peroxides, such as di-tert-butyl peroxide or dicumyl peroxide. The azo compounds used are basically 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), and 2,2'-azobis(amidinylpropyl) dihydrochloride (AIBA, corresponding to V-50 from Wako Chemicals). Suitable oxidants for redox initiator systems are essentially the peroxides mentioned above. Corresponding reducing agents that can be used are sulfur compounds with low oxidation states, such as alkali metal sulfites, for example, potassium sulfite and / or sodium sulfite; alkali metal bisulfites, for example, potassium bisulfite and / or sodium bisulfite; alkali metal metabisulfites, for example, potassium metabisulfite and / or sodium metabisulfite; formaldehyde bisulfite, for example, potassium formaldehyde bisulfite and / or sodium formaldehyde bisulfite; alkali metal salts, especially potassium and / or sodium salts of aliphatic sulfinic acids and alkali metal hydrides, for example, potassium hydrosulfide and / or sodium hydrosulfide; salts of polyvalent metals, such as ferric(II) sulfate, ammonium ferric(II) sulfate, ferric(II) phosphate; ethylene glycols, such as dihydroxymaleic acid, benzoin and / or ascorbic acid; and reducing sugars, such as sorbitol, glucose, fructose and / or dihydroxyacetone.

[0170] Preferred free radical initiators are inorganic peroxides, especially peroxydisulfate.

[0171] Generally speaking, the amount of free radical initiator used is from 0.05% to 2% by weight based on the total amount of monomer M, preferably from 0.1% to 1% by weight based on the total amount of monomer M.

[0172] The amount of free radical initiator required for the emulsion polymerization of monomer M can initially be fully loaded into the polymerization vessel. However, it is also possible to load no initiator or only a portion, for example, no more than 30% by weight, particularly no more than 20% by weight, based on the total amount of free radical initiator, and then add any remaining amount of free radical initiator to the free radical polymerization reaction under polymerization conditions. Preferably, at least 70%, particularly at least 80%, particularly at least 90%, or the total amount of polymerization initiator, is added to the free radical polymerization reaction under polymerization conditions. The addition can be carried out in batches of one or more portions according to consumption during the free radical emulsion polymerization of monomer M, or continuously at a constant or varying flow rate.

[0173] Generally, the term "polymerization conditions" should be understood to refer to the temperatures and pressures at which free radical-initiated aqueous emulsion polymerization proceeds at a sufficient polymerization rate. These conditions are particularly dependent on the free radical initiator used. Advantageously, the type and amount of free radical initiator, polymerization temperature, and polymerization pressure are chosen such that a sufficient amount of initiating free radicals is always present to initiate or sustain the polymerization reaction.

[0174] Preferably, the free radical emulsion polymerization of monomer M is carried out by a so-called feed method (also known as a monomer feed method), which means that at least 80%, particularly at least 90%, of the total amount of monomer M to be polymerized, or metered addition to the polymerization reaction during metering period P under polymerization conditions. The addition can be carried out in batches, and preferably continuously at a constant or varying feed rate. The duration of period P can depend on the production equipment and can vary, for example, from 20 minutes to 12 hours. Typically, the duration of period P will be in the range of 0.5 hours to 8 hours, particularly 1 hour to 6 hours. In multi-stage emulsion polymerization steps, the total duration of all steps is typically within the above range. The duration of each individual step is typically shorter.

[0175] Preferably, at least 70%, particularly at least 80%, especially at least 90% or the total amount of polymerization initiator is introduced into the emulsion polymerization along with the addition of monomers.

[0176] Aqueous free radical emulsion polymerization is typically carried out in the presence of one or more suitable surfactants. These surfactants typically contain emulsifiers and provide micelles in which polymerization occurs, and these micelles serve to stabilize monomer droplets and promote polymer particle growth during aqueous emulsion polymerization. The surfactants used in emulsion polymerization are generally not separated from the polymer dispersion but are retained in the aqueous polymer dispersion obtainable by emulsion polymerization of monomer M.

[0177] Surfactants can be selected from emulsifiers and protective colloids. In contrast to emulsifiers, protective colloids should be understood as polymeric compounds with a molecular weight higher than 2000 Daltons, while emulsifiers typically have a lower molecular weight. Surfactants can be anionic surfactants, nonionic surfactants, or mixtures of nonionic and anionic surfactants.

[0178] Anionic surfactants typically have at least one anionic group, usually selected from phosphate, phosphonate, sulfate, and sulfonate groups. Anionic surfactants with at least one anionic group are typically used in the form of their alkali metal salts, especially their sodium salts, or in the form of their ammonium salts.

[0179] Preferred anionic surfactants are anionic emulsifiers, particularly those with at least one sulfate or sulfonate group. Similarly, anionic emulsifiers with at least one phosphate or phosphonate group can be used as the sole anionic emulsifier or in combination with one or more anionic emulsifiers with at least one sulfate or sulfonate group.

[0180] Examples of anionic emulsifiers having at least one sulfate or sulfonate group are, for example,

[0181] -Alkyl sulfates, especially C8-C 22 -Salts of alkyl sulfates, especially alkali metal salts and ammonium salts

[0182] -Ethoxylated alkanol sulfate monoesters, particularly preferably ethoxylated C8-C having an ethoxylation level (EO level) in the range of 2 to 40. 22 Salts of sulfate monoesters of alkyl alcohols, especially alkali metal salts and ammonium salts.

[0183] -Ethoxylated alkylphenol sulfate monoesters, especially ethoxylated C4-C 18 Salts of sulfate monoesters of alkylphenols (preferably with an EO level of 3 to 40), especially alkali metal salts and ammonium salts.

[0184] -alkyl sulfonic acids, especially C8-C 22 Salts of alkyl sulfonic acids, especially alkali metal salts and ammonium salts.

[0185] Dialkyl esters of sulfosuccinic acid, especially di-C4-C 18 Salts of alkyl esters, especially alkali metal salts and ammonium salts.

[0186] -alkylbenzene sulfonic acids, especially C4-C 22 Salts of alkylbenzene sulfonic acids, especially alkali metal salts and ammonium salts, and

[0187] - Monosulfonated or disulfonated alkyl-substituted diphenyl ethers, for example, having a C4-C on one or both aromatic rings. 24 Salts of alkyl-group bis(benzenesulfonic acid) ethers, especially alkali metal salts and ammonium salts. The latter are well known, for example from US-A-4,269,749, and are commercially available, for example as Dowfax. ® 2A1 (Dow Chemical Company).

[0188] A mixture of the above salts is also suitable.

[0189] Examples of anionic emulsifiers containing phosphate or phosphonate groups include, but are not limited to, the following salts selected from the group consisting of:

[0190] - Monoalkyl phosphates and dialkyl phosphates, especially C8-C phosphates 22 Salts of alkyl esters, especially alkali metal salts and ammonium salts.

[0191] - Preferably, phosphate monoesters of C2-C3-alkoxylated alkanols having an alkoxylation level in the range of 2 to 40, particularly in the range of 3 to 30, such as ethoxylated C8-C... 22 -Alkyl phosphate monoesters, preferably propoxylated C8-C having a propoxylation level (PO level) in the range of 2 to 40. 22 -Alkyl phosphate monoesters and preferably ethoxylated-co-propoxylated C8-C having an ethoxylation level (EO level) in the range of 1 to 20 and a propoxylation level in the range of 1 to 20. 22 Salts of phosphate monoesters of alkyl alcohols, especially alkali metal salts and ammonium salts.

[0192] - Phosphate monoesters of ethoxylated alkylphenols, especially ethoxylated C4-C 18 Salts of alkylphenol (preferably EO levels of 3 to 40) phosphate monoesters, especially alkali metal salts and ammonium salts.

[0193] -alkylphosphonic acids, especially C8-C 22 Salts of alkylphosphonic acids, especially alkali metal salts and ammonium salts, and

[0194] -alkylphenylphosphonic acids, especially C4-C 22 Salts of alkylphenylphosphonic acids, especially alkali metal salts and ammonium salts.

[0195] Other suitable anionic surfactants can be found in Houben-Weyl, Methoden der organischenChemie [Methods of Organic Chemistry], Vol. XIV / 1, Makromolekulare Stoffe [Macromolecular Substances], Georg-Thieme-Verlag, Stuttgart, 1961, pp. 192-208.

[0196] Preferably, the surfactant comprises at least one anionic emulsifier having at least one sulfate or sulfonate group. The at least one anionic emulsifier having at least one sulfate or sulfonate group can be the only type of anionic emulsifier. However, a mixture of at least one anionic emulsifier having at least one sulfate or sulfonate group and at least one anionic emulsifier having at least one phosphate or phosphonate group can also be used. In such mixtures, the amount of the at least one anionic emulsifier having at least one sulfate or sulfonate group is preferably at least 50% by weight based on the total weight of the anionic surfactant used in the method of the present invention. Specifically, the amount of the anionic emulsifier having at least one phosphate or phosphonate group is no more than 20% by weight based on the total weight of the anionic surfactant used in the method of the present invention.

[0197] Preferred anionic surfactants are anionic emulsifiers selected from the group consisting of, or mixtures thereof:

[0198] -Alkyl sulfates, especially C8-C 22 -Salts of alkyl sulfates, especially alkali metal salts and ammonium salts

[0199] -Ethoxylated alkanol sulfate monoesters, particularly preferably ethoxylated C8-C having an ethoxylation level (EO level) in the range of 2 to 40. 22 Salts of sulfate monoesters of alkyl alcohols, especially alkali metal salts.

[0200] -Ethoxylated alkylphenol sulfate monoesters, especially ethoxylated C4-C 18 -Alkylphenol (EO level preferably 3 to 40) sulfate monoesters,

[0201] -alkylbenzene sulfonic acids, especially C4-C 22 -alkylbenzene sulfonic acid, and

[0202] - Monosulfonated or disulfonated alkyl-substituted diphenyl ethers, for example, having a C4-C on one or both aromatic rings. 24 bis(benzenesulfonic acid) ethers with alkyl groups.

[0203] Particularly preferred are anionic emulsifiers selected from the group consisting of, and mixtures thereof:

[0204] -Alkyl sulfates, especially C8-C 22 -Salts of alkyl sulfates, especially alkali metal salts and ammonium salts

[0205] -Ethoxylated alkanol sulfate monoesters, particularly preferably ethoxylated C8-C having an ethoxylation level (EO level) in the range of 2 to 40. 22 Salts of sulfate monoesters of alkyl alcohols, especially alkali metal salts.

[0206] - Monosulfonated or disulfonated alkyl-substituted diphenyl ethers, for example, having a C4-C on one or both aromatic rings. 24 bis(benzenesulfonic acid) ethers with alkyl groups.

[0207] The surfactant, together with the aforementioned anionic surfactant, may also include one or more nonionic surfactants, particularly selected from nonionic emulsifiers. Suitable nonionic emulsifiers are, for example, aryl aliphatic or aliphatic nonionic emulsifiers, such as ethoxylated mono-, di-, and trialkylphenols (EO level: 3 to 50, alkyl group: C4-C). 10 ), ethoxylated long-chain alcohols (EO level: 3 to 100, alkyl group: C8-C) 36 ) and poly(ethylene oxide) / poly(propylene oxide) homopolymers and copolymers. These may contain alkylene oxide units copolymerized in a random or block form. A very suitable example is an EO / PO block copolymer. Preferred are ethoxylated long-chain alkanols, particularly those with alkyl groups C8-C. 30 Those ethoxylated compounds with an average ethoxylation level of 5 to 100, and particularly preferred among them are those having a straight-chain C 12 -C 20 Those ethoxylated compounds with alkyl groups and an average ethoxylation level of 10 to 50, as well as ethoxylated monoalkylphenols.

[0208] In one specific embodiment of the invention, based on the total amount of surfactant used in the method of the invention, the surfactant used in the method of the invention comprises less than 20% by weight, especially not more than 10% by weight of nonionic surfactant, and especially does not contain any nonionic surfactant.

[0209] Preferably, the amount of surfactant used is in the range of 0.2 wt% to 5 wt%, particularly in the range of 0.3 wt% to 3 wt%, based on the monomer M to be polymerized. In multi-step emulsion polymerization, the amount of surfactant used is typically in the range of 0.2 wt% to 5 wt%, particularly in the range of 0.3 wt% to 3 wt%, based on the total amount of monomer polymerized in the respective steps.

[0210] Preferably, a majority (i.e., at least 80% of the emulsifier used) is added to the emulsion polymerization at the same time as the monomer. In particular, the monomer is added to the polymerization reaction as an aqueous emulsion containing at least 80% of the surfactant used in the emulsion polymerization.

[0211] It has been found advantageous to carry out free radical emulsion polymerization of monomer M in the presence of a seed latex. The seed latex is the polymer latex present in the aqueous polymerization medium prior to the initiation of polymerization of monomer M. The seed latex can facilitate better control of particle size or the final polymer latex obtained in the free radical emulsion polymerization of this invention.

[0212] In principle, any polymer latex can be used as a seed latex. For the purposes of this invention, a seed latex is preferred, wherein the polymer particles have a relatively small particle size. Specifically, the Z-mean particle size of the polymer particles in the seed latex (as measured by dynamic light scattering (DLS) at 20°C (see below)) is preferably in the range of 10 nm to 80 nm, particularly 10 nm to 50 nm. Preferably, the polymer particles of the seed latex are made of olefinically unsaturated monomers comprising at least 95% by weight of one or more monomers Mb1 and / or Mb2 as defined above, based on the total weight of the monomers forming the seed latex.

[0213] Therefore, the seed latex is typically loaded into the polymerization vessel before the polymerization of monomer M begins. Specifically, the seed latex is loaded into the polymerization vessel, and polymerization conditions are subsequently established, for example, by heating the mixture to the polymerization temperature. It may be advantageous to load at least a portion of the radical initiator into the polymerization vessel before adding monomer M. However, monomer M and the radical polymerization initiator can also be added to the polymerization vessel in parallel.

[0214] The amount of seed latex in solid form is typically in the range of 0.05% to 5% by weight, particularly 0.1% to 3% by weight, based on the total weight of the monomers in the monomer composition M to be polymerized.

[0215] If the free radical aqueous emulsion polymerization is carried out as the free radical multi-step aqueous emulsion polymerization of the present invention, the second step is performed after the first step. The second step can be performed immediately after the monomer composition of the first step has been completely added to the emulsion polymerization of the first step; that is, the polymerization of the monomer to be polymerized in the second step begins immediately after the addition of the monomer to be polymerized in the first step is completed. However, the polymerization of the first step can also continue after the addition of the monomer to be polymerized in the first step has been completed, but before the polymerization of the monomer to be polymerized in the second step begins.

[0216] In the second step and any additional steps of multi-step emulsion polymerization, the monomer can be added all at once to the polymer dispersion obtained in the first step. However, the free radical emulsion polymerization of the monomer to be polymerized in the second step is preferably carried out by the feeding method described above. This means that during the metering time period P', at least 80%, particularly at least 90%, or all of the monomer to be polymerized in the second step and any additional steps is metered into the polymerization reaction under the polymerization conditions. The duration of each of the time periods P and P' can depend on the production equipment and can vary, for example, from 10 minutes to 8 hours. Typically, the duration of each of the time periods P and P' will be in the range of 20 minutes to 7 hours, particularly 30 minutes to 5 hours.

[0217] The free radical aqueous emulsion polymerization of the present invention can be carried out at temperatures ranging from 0°C to 170°C. The temperatures used are typically in the range of 50°C to 120°C, often in the range of 60°C to 120°C, and frequently in the range of 70°C to 110°C. The free radical aqueous emulsion polymerization of the present invention can be carried out at pressures less than, equal to, or greater than 1 atm (atmosphere), and therefore the polymerization temperature can exceed 100°C and can reach up to 170°C. The polymerization of monomers is typically carried out at ambient pressure, but can also be carried out at elevated pressures. In this case, the pressure can be 1.2 bar, 1.5 bar, 2 bar, 5 bar, 10 bar, 15 bar (absolute) or even higher. If the emulsion polymerization is carried out under reduced pressure, pressures of 950 mbar, typically 900 mbar, and often 850 mbar (absolute) are established. Advantageously, the free radical aqueous emulsion polymerization of the present invention is carried out at an ambient pressure (about 1 atm) excluding oxygen, for example, under an inert gas atmosphere, such as nitrogen or argon.

[0218] The free radical emulsion polymerization of the present invention is typically carried out in an aqueous polymerization medium that, together with water, includes at least one surfactant to stabilize the monomer emulsion and the polymer particles of the polymer latex. Suitable surfactants are mentioned above.

[0219] In addition, the conditions required for free radical emulsion polymerization are well known to those skilled in the art, for example from the prior art cited at the beginning and from "Emulsionspolymerization" [EmulsionPolymerization], in Encyclopedia of Polymer Science and Engineering, Vol. 8, p. 659 and subsequent pages (1987); DC Blackley, in High Polymer Latices, Vol. 1, p. 35 and subsequent pages (1966); H. Warson, The Applications of Synthetic Resin Emulsions, Chapter 5, p. 246 and subsequent pages (1972); D. Diederich, Chemie in unserer Zeit, 24, pp. 135-142 (1990); Emulsion Polymerization, Interscience Publishers, New York (1965); DE-A 40 03 422, and Dispersionen synthetischer Hochpolymerer [Dispersions of Synthetic HighPolymers], F. Hölscher, Springer-Verlag, Berlin (1969)].

[0220] It is generally advantageous to post-process the aqueous polymer dispersion obtained upon completion of polymerization of monomer M to reduce the residual monomer content. This post-processing can be carried out chemically, for example by using a more efficient free radical initiator system to complete the polymerization reaction (referred to as post-polymerization), and / or physically, for example by stripping the aqueous polymer dispersion with steam or an inert gas. Corresponding chemical and physical methods are well known to those skilled in the art, see, for example, EP-A771328, DE-A 19624299, DE-A 19621027, DE-A 19741184, DE-A 19741187, DE-A 19805122, DE-A 19828183, DE-A 19839199, DE-A 19840586, and DE-A 19847115. The combination of chemical and physical post-treatment has the advantage of removing not only unconverted olefinic unsaturated monomers from aqueous polymer dispersions, but also other damaging volatile organic compounds (VOCs).

[0221] Because the polymer contained in the aqueous polymer dispersion contains acidic groups from the monomer Ma2 and optionally from the polymerization initiator, the aqueous polymer dispersion obtained by the method of the present invention is typically neutralized before being formulated into a coating composition. The neutralization of the acidic groups of the polymer is achieved after polymerization and / or during polymerization using a neutralizing agent known to those skilled in the art. For example, the neutralizing agent may be added in a co-feed with the monomer to be polymerized or in a separate feed. Suitable neutralizing agents include organic amines, alkali metal hydroxides, and ammonium hydroxide. In particular, neutralization is achieved by using ammonia or alkali metal hydroxides (such as sodium hydroxide or potassium hydroxide).

[0222] Preferably, the final polymer dispersion has a pH of at least 7, for example, in the pH range of 7 to 12, before being used in the coating composition.

[0223] The aqueous polymer dispersions of the present invention are particularly useful as binders or co-binders in aqueous coating compositions, especially architectural coating compositions and coating compositions for mineral molded bodies.

[0224] Waterborne coating compositions typically contain the waterborne polymer dispersion of the present invention, and thus contain a polymer in the form of fine particles obtained by polymerization of monomer M, as well as surfactants for emulsion polymerization, such as emulsifiers and / or protective colloids.

[0225] Waterborne coating compositions typically contain no more than 50% by weight, more particularly no more than 20% by weight, and especially no more than 10% by weight, of a water-miscible solvent based on the total weight of the coating composition. Very particularly preferably, the formulations of the present invention do not contain any organic solvents other than water, except for typical anti-frost agents and film-forming aids.

[0226] The aqueous polymer dispersion of the present invention can be used directly as a coating composition. However, the coating composition may contain typical formulation adjuvants. The total amount of typical formulation adjuvants is generally in the range of 0.1% to 30% by weight of the aqueous coating composition, particularly in the range of 0.5% to 10% by weight.

[0227] Conventional formulation adjuvants include, but are not limited to, pigment dispersants, wetting agents, rheology modifiers, leveling agents, bactericides, defoamers, antifreeze agents, flow promoters, and the aforementioned film-forming aids. Other suitable formulation adjuvants and components are described, for example, by J. Bieleman in “Additives for Coatings,” Wiley-VCH, Weinheim 2000; by TCPatton in “Paint Flow and Pigment Dispersions,” 2nd edition, John Wiley & Sons 1978; and by M. Schwartz and R. Baumstark in “Water based Acrylates for Decorative Coatings,” Curt R. Vincentz Verlag, Hanover 2001.

[0228] Furthermore, the waterborne coating compositions of the present invention may also contain inorganic fillers and / or pigments. Typical pigments are, for example, titanium dioxide (preferably in rutile form), barium sulfate, zinc oxide, or zinc barium white (zinc sulfide + barium sulfate). For decorative purposes, the formulation may also contain colored pigments such as iron oxide, carbon black, graphite, zinc yellow, zinc green, ultramarine, manganese black, antimony black, manganese violet, Paris blue, or Schweinfurt green. The formulation may also contain pigments that reflect IR radiation, i.e., IR-reflective pigments, such as pigments based on Fe / Cr mixed oxides and titanium-based mixed oxides (such as antimony nickel titanium oxide). Suitable fillers include aluminosilicates, such as feldspar; silicates, such as kaolin, talc, mica, magnesite; alkaline earth metal carbonates, such as calcium carbonate (e.g., in calcite or chalk form), magnesium carbonate, dolomite; alkaline earth metal sulfates, such as calcium sulfate; silicon dioxide, etc.

[0229] The proportions of pigments and fillers in a waterborne coating composition can be described in a manner known per se via pigment volume concentration (PVC). PVC describes the ratio of the volume of pigment (VP) and filler (VF) to the total volume, which consists of the volumes of binder (VB), pigment (VP), and filler (VF) in a dried coating film, expressed as a percentage: PVC = (VP + VF) x 100 / (VP + VF + VB). Preferably, PVC will not exceed a value of 60, and specifically within the range of 0 to 50.

[0230] The aqueous coating compositions of the present invention may also contain crosslinking additives. Such additives include: aromatic ketones, such as alkylphenyl ketones, which, if suitable, have one or more substituents on the benzene ring; or benzophenones and substituted benzophenones as photoinitiators. Photoinitiators suitable for this purpose are known, for example, by DE-A 38 27 975 and EP-A 417 568. If the polymer formed from the polymerized monomer M comprises a monomer containing a carbonyl group in copolymer form, suitable compounds for crosslinking are also water-soluble compounds having at least two amino groups, an example being a dihydrazide of an aliphatic dicarboxylic acid according to DE-A 39 01073.

[0231] The waterborne coating compositions of the present invention include, for example, transparent coating (transparent varnish) formulations, surface coating formulations, such as paints, plasters or coating systems.

[0232] According to a preferred embodiment of the invention, the waterborne coating composition is formulated as a transparent coating material. In this case, these waterborne coating compositions typically contain 10% to 60% by weight, preferably 40% to 55% by weight, of at least one polymer formed from a polymerized monomer M, based on their total weight, and 0.1% to 30% by weight, preferably 0.5% to 10% by weight, of typical additives, more particularly defoamers and / or film-forming aids.

[0233] Another embodiment of the invention relates to an aqueous coating composition in the form of a coloring and / or filling formulation. In this case, the total amount of the polymer formed from the polymerized monomer M in the aqueous formulation ranges from 10% to 60% by weight, preferably from 20% to 40% by weight; the content of the additives ranges from 0.1% to 30% by weight, and preferably from 0.5% to 10% by weight; and the content of the filler and / or pigments ranges from 0% to 50% by weight, and more specifically from 0% to 40% by weight. Preferably, the PVC content ranges from 0% to 30%, more preferably from 0% to 10%. Furthermore, in addition to film-forming aids and defoamers, the coloring formulation will preferably also contain dispersants and / or wetting agents.

[0234] The transparent coating materials and colored paints of the present invention may contain additional typical additives, such as wetting agents, in-can and in-film preservatives, thickeners, defoamers, flow promoters and antifreeze agents, in amounts typically present in themselves.

[0235] The present invention also relates to the use of the aqueous coating composition of the present invention for permanently coating a substrate, and therefore to a method for producing a permanent coating on the surface of a substrate. The method includes...

[0236] (a) Applying the aqueous coating composition according to the invention to the surface to be coated, and

[0237] (b) Dry the composition to produce a permanent coating.

[0238] Waterborne coating compositions can be applied to the surface and / or substrate to be coated in conventional ways, such as by brushing or rolling, spraying, dipping, rolling, curtain coating, or rod coating. Coating of the surface and / or substrate is carried out in such a manner that the surface and / or substrate are first coated with the composition of the present invention, and then the waterborne composition undergoes a drying step. The drying step is typically performed in a temperature range of +5°C to +80°C, particularly in the range of +10°C to +70°C. Generally, temperatures of +5°C to +25°C are sufficient to achieve an acceptable permanent coating. However, higher temperatures will accelerate the drying process, and temperatures up to +80°C or up to +70°C may also be suitable.

[0239] In principle, the water-based coating compositions of the present invention can be applied to any substrate that is typically coated with a water-based coating composition. The water-based coating compositions can be applied to surfaces such as, for example, metals, asphalt, concrete, fiber cement board, stone, ceramics, minerals, wood, plastics, polymers, and glass. The water-based coating compositions can be applied to interior or exterior surfaces, such as, for example, architectural surfaces, such as roofs, walls, floors, and ceilings.

[0240] The waterborne coating compositions of the present invention are particularly suitable for coating mineral substrates, including stone walls and concrete surfaces, and especially suitable for coating the surfaces of molded mineral products, such as concrete roof tiles and fiber cement boards.

[0241] It is well known to coat molded mineral articles with water-based coating compositions, for example, from the prior art discussed at the beginning and from EP 1069093 and EP 3498783. In the case of coating molded mineral articles, the application rate of the water-based polymer formulation to be applied for corrosion protection is typically 50 g / m³. 2 Up to 700g / m 2(Wet basis). It can be applied in a conventional manner by spraying, troweling, scraping, rolling, or pouring (including curtain coating). The method of the present invention can be used for cured and newly prepared (“green”) molded mineral products. It is particularly suitable for preserving molded mineral products (cast concrete) containing cement as a mineral binder. In a particularly advantageous way, it prevents frost formation on concrete roof tiles. The latter are typically made of cement mortar, the consistency of which allows for final molding. They typically harden at temperatures between 40°C and 80°C. Curing usually takes place at a relative humidity in the range of 30% to 90%. After molding (e.g., by extrusion), but usually before curing, the concrete roof tiles are coated with the aqueous coating composition of the present invention and then stored in a curing chamber for 6 to 12 hours, where the aforementioned temperature and humidity conditions typically prevail. During this time, they cure, and simultaneously the coating composition forms a permanent film. In some cases, after the curing operation, further application of the coating composition is made, followed by drying. Then, drying can be carried out at the above-mentioned temperature, for example, in the range of 5°C to 50°C.

[0242] Example

[0243] The following abbreviations will be used in the following text:

[0244] % bw weight%

[0245] AA acrylic acid

[0246] AMA allyl methacrylate

[0247] AMPS: 2-Acrylamido-2-methylpropanesulfonic acid

[0248] AM Acrylamide

[0249] BDG Butyl diethylene glycol

[0250] DLS: Dynamic Light Scattering

[0251] EHTG 2-Ethylhexyl mercaptoacetate

[0252] EO: Ethylene oxide

[0253] HDC: Fluid Dynamics Chromatography

[0254] HDC-PS: Particle size determined by HDC

[0255] HEMA: Hydroxyethyl methacrylate

[0256] HPPS: High-performance particle size analyzer

[0257] IA itaconic acid

[0258] MAA: Methacrylic acid

[0259] MAM: Methacrylamide

[0260] nd not determined

[0261] No observations were observed.

[0262] n-BuA n-Butyl acrylate

[0263] PDI: Multidispersion Index

[0264] rpm: revolutions per minute

[0265] SC: Solid content

[0266] SDS: Sodium lauryl sulfate (Sodium lauryl sulfate)

[0267] t-DMK tert-dodecyl mercaptan

[0268] MEMO3-(trimethoxysilyl)propyl methacrylate

[0269] WU: Water Absorption Rate

[0270] Z-PS: Particle size determined by DLS

[0271] 1. Analysis and Characterization

[0272] 1.1 Characterization of Dispersions

[0273] i) Measure the solids content of the polymer dispersion according to the standard method DIN EN ISO 3251: 2008-06.

[0274] ii) Measure the pH value of the polymer dispersion according to the standard method DIN EN 1262:2004-01.

[0275] iii) The glass transition temperature was determined by means of a DSC instrument (Q 2000 series from TA Instruments) using the DSC method (differential scanning calorimetry, 20 K / min, midpoint measurement, DIN 53765:1994-03).

[0276] iv) Particle size distribution of polymer dispersions as measured by DLS

[0277] The particle size of the polymer latex was determined by dynamic light scattering (DLS, also known as quasi-elastic light scattering) of an aqueous polymer dispersion diluted with deionized water to 0.001 wt% to 0.5 wt% at 22 °C using HPPS from Malvern Instruments, England. The cumulative Z-mean diameter calculated from the measured autocorrelation function is reported (ISO Standard 13321).

[0278] v) Particle size distribution of polymer dispersion as measured by HDC

[0279] Measurements were performed using a PL-PSDA particle size distribution analyzer (Polymer Laboratories, Inc.). A small amount of polymer latex sample was injected into an aqueous eluent containing an emulsifier to obtain a concentration of approximately 0.5 g / L. The mixture was pumped through a glass capillary approximately 15 mm in diameter filled with polystyrene spheres. As determined by their hydrodynamic diameter, smaller particles could spatially enter slower-flowing regions within the capillary, resulting in, on average, smaller particles experiencing slower elution flow. Finally, fractionation was monitored using a UV detector that measures extinction at a fixed wavelength of 254 nm.

[0280] vi) Determine the minimum film-forming temperature (MFFT) using a Kofler heating stage according to DIN ISO 2115:2001-04.

[0281] 1.2 Adjustment of Dispersions and Preparation of Transparent and Colored Coatings

[0282] The latex sample from Section 3 was adjusted with approximately 10% by weight of BDG based on the latex polymer solids content to achieve a minimum film-forming temperature of 5°C to 10°C. Other coalescing agents, such as diisobutyl adipate, may also be used. Tego Foamex 822 (0.2%), an optional sodium hydroxide (2%), and water were added to adjust the pH to 7-8, and water was added to adjust for the desired solids content to produce the clear coating mentioned in Section 1.5. To obtain the PVC 2 coating composition, 90% by weight of the clear coating and 10% by weight of a pigment paste prepared from 50% by weight of water and 50% by weight of Bayferrox red 110 (Lanxess AG, Leverkusen) were mixed by vigorous stirring. The flow time was determined using a Ford cup (No. 4).

[0283] 1.3 Water absorption rate :

[0284] A slightly colored coating, as described in 1.2 of the above examples, was cast onto polyethylene foil using a scraper with a 600µm gap width. The resulting film was dried at room temperature for 24 hours. Afterward, the film was separated from the polyethylene foil and dried in an oven at 60°C for three days. Two samples, each 5cm x 4cm, were cut from the film using a gauge. The samples were immersed in a stainless steel mesh in a reservoir of deionized water for 72 hours. The samples were then removed from the stainless steel mesh and dried in an oven at 60°C to constant weight and weighed (w). 干 Then, the sample was placed again in the stainless steel mesh of the deionized water reservoir for 24 hours, removed from the reservoir and mesh, and dried with a towel to remove all adhering water droplets. It was then weighed again immediately (w 湿 The water absorption rate, expressed as a percentage (%), is calculated using the following formula.

[0285] .

[0286] 1.4 Preparation of Concrete Roofing Tiles

[0287] Concrete roofing tiles are produced by extruding the concrete admixtures described in Table 1. The extruded tiles have dimensions of 30*20*1.8cm. After extrusion, a single first coating is applied, and the tiles are cured in a humidity-controlled oven using a temperature gradient from 25°C to 50°C at 95% humidity for 4 hours. After this period, a second coating can be applied immediately, and the tiles are allowed to cool to room temperature.

[0288] Table 1: Concrete Mixtures :

[0289]

[0290] Mix components 1-5 in a concrete mixer.

[0291] 1.5 Application of Coating

[0292] Using a SATA manual spray gun with a 1.7mm nozzle, immediately (after 15 to 90 seconds) spray the newly extruded roofing tiles with the PVC2 coating composition from the chapter. Apply 8-10g of coating to a 600cm² surface. After curing for 4 hours, apply an additional 5-10g of clear coating to the roofing tiles, then allow the tiles to cool to ambient temperature. Alternatively, do not apply a second coat of coating. Test both double-layer and single-layer coatings.

[0293] 1.6 Testing of the properties of the coating applied to the tile

[0294] After curing and cooling the coated roof tile samples to ambient temperature, the tiles were exposed to water vapor for five days, starting the day after the curing process. This was done by placing the tile with the coated side on a water bath maintained at 60°C, with the water bath opening completely covered, meaning water vapor condensed on the coated substrate and could not pass through. Immediately after removing the tiles from the bath, they were visually assessed for whitening upon contact with water on a scale of 0 (none), 1 (very weak), 2 (weak), 3 (medium), 4 (strong), and 5 (very strong). After the coating had completely re-dried (24 hours), cracking and color changes were assessed using the same grading system from 0 to 5. For all three parameters, 0 was the best grade, and 5 was the worst.

[0295] 2. Materials used to prepare polymer dispersions

[0296] - Seed latex S1: Acrylic seed particles with a solids content of 33% by weight and a Z-average particle size of 30 nm as determined by DLS.

[0297] - Emulsifier A: Sodium salt of C12 / 14 alcohol ether sulfate having about 2 EO units, 28% by weight aqueous solution.

[0298] - Emulsifier B: Sodium dodecyl sulfate, 15% by weight, aqueous solution.

[0299] - Emulsifier C: A 20% by weight aqueous solution of a C16 / 18 alcohol ethoxylate having approximately 18 EO units.

[0300] - Emulsifier D: Disodium lauryl phenyl ether disulfonate (Dowfax) ® 2A1 (Dow Chemical Company, USA))

[0301] Unless otherwise stated, the water used in the preparation examples is deionized water.

[0302] 3. Preparation of polymer dispersions

[0303] Comparative Example C1 :

[0304] The synthesis was carried out as follows: Emulsion A was prepared by mixing 27.00 g emulsifier A, 28.00 g emulsifier C, 2.00 g sodium bicarbonate, 73.33 g methacrylamide (15% aqueous solution), 11.00 g sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 594.00 g methyl methacrylate, 506.00 g n-butyl acrylate and 362.81 g deionized water.

[0305] Initiator solution I was prepared by dissolving 0.59 g of sodium peroxide in 11.00 g of deionized water.

[0306] Initiator solution II was prepared by dissolving 3.00 g of sodium peroxide in 39.85 g of deionized water.

[0307] 583.00g of deionized water and 6.00g of emulsifier A were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 80°C.

[0308] After reaching a reaction temperature of 80°C, 4% of emulsion A is added to the reaction vessel within 5 minutes. Then, initiator I is added to the reaction vessel and polymerization continues for 15 minutes. The remaining emulsion A is then fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution II is fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0309] After the addition of emulsion A and initiator solution II was completed, the reaction vessel was stirred for another 60 minutes and finally cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0310] Comparative Example C2 :

[0311] The synthesis was carried out as follows: Emulsion A was prepared by mixing 27.00 g of emulsifier A, 28.00 g of emulsifier C, 2.00 g of sodium bicarbonate, 55.00 g of methacrylamide (15% aqueous solution), 16.50 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 594.50 g of methyl methacrylate, 506.00 g of n-butyl acrylate and 375.64 g of deionized water.

[0312] Initiator solution I was prepared by dissolving 0.59 g of sodium peroxide in 11.00 g of deionized water.

[0313] Initiator solution II was prepared by dissolving 3.00 g of sodium peroxide in 39.85 g of deionized water.

[0314] 583.00g of deionized water and 6.00g of emulsifier A were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 80°C.

[0315] After reaching a reaction temperature of 80°C, 4% of emulsion A is added to the reaction vessel within 5 minutes. Then, initiator I is added to the reaction vessel and polymerization continues for 15 minutes. The remaining emulsion A is then fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution II is fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0316] After the addition of emulsion A and initiator solution II was completed, the reaction vessel was stirred for another 60 minutes and finally cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0317] Comparative example C3 :

[0318] The synthesis was carried out as follows: Emulsion A was prepared by mixing 27.00 g of emulsifier A, 28.00 g of emulsifier C, 2.00 g of sodium bicarbonate, 46.67 g of methacrylamide (15% aqueous solution), 18.00 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 594.50 g of methyl methacrylate, 506.00 g of n-butyl acrylate and 381.97 g of deionized water.

[0319] Initiator solution I was prepared by dissolving 0.59 g of sodium peroxide in 11.00 g of deionized water.

[0320] Initiator solution II was prepared by dissolving 3.00 g of sodium peroxide in 39.85 g of deionized water.

[0321] 583.00g of deionized water and 6.00g of emulsifier A were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 80°C.

[0322] After reaching a reaction temperature of 80°C, 4% of emulsion A is added to the reaction vessel within 5 minutes. Then, initiator I is added to the reaction vessel and polymerization continues for 15 minutes. The remaining emulsion A is then fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution II is fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0323] After the addition of emulsion A and initiator solution II was completed, the reaction vessel was stirred for another 60 minutes and finally cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0324] Comparative Example C4 :

[0325] The synthesis was carried out as follows: Emulsion A was prepared by mixing 33.06 g of emulsifier D (Dowfax 2A1; 45% aqueous solution), 18.41 g of emulsifier C, 6.00 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 12.31 g of acrylamide (50% aqueous solution), 640.22 g of methyl methacrylate, 591.25 g of n-butyl acrylate and 524.13 g of deionized water.

[0326] Initiator solution I was prepared by dissolving 2.84 g of sodium peroxide in 37.79 g of deionized water.

[0327] Initiator solution II was prepared by dissolving 0.47 g of sodium peroxide in 6.29 g of deionized water.

[0328] Oxidizing solution O was prepared by dissolving 1.11 g of tert-butyl hydroperoxide in 10.04 g of deionized water.

[0329] A reducing solution R was prepared by dissolving 0.87 g of acetone and sodium bisulfite in 7.80 g of deionized water.

[0330] 512.11 g of deionized water and 32.20 g of seed latex S1 were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 90°C.

[0331] After reaching a reaction temperature of 90°C, 18.75 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution) was added to the reaction vessel. Then, emulsion A was fed into the reaction vessel over 180 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 180 minutes.

[0332] Then, initiator solution II was fed into the reaction vessel over 30 minutes and stirred for another 30 minutes. Next, simultaneously but spatially separate feed vessels were used to feed oxidizing solution O and reducing solution R into the reaction vessel over 60 minutes. Then, 15.58 g of deionized water was added to the reaction vessel. Finally, 35.11 g of deionized water was added to the reaction vessel and the mixture was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0333] Comparative Example C5 :

[0334] The synthesis was carried out as follows: Emulsion A was prepared by mixing 39.73 g of emulsifier A, 24.72 g of emulsifier B, 1.18 g of 3-(trimethoxysilyl)propyl methacrylate, 30.90 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 10.51 g of acrylic acid, 680.68 g of methyl methacrylate, 528.19 g of n-butyl acrylate and 667.38 g of deionized water.

[0335] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0336] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0337] The reducing solution R was prepared by dissolving 1.47 g of sodium acetone-sodium bisulfite in 9.66 g of deionized water.

[0338] 569.41 g of deionized water and 41.20 g of seed latex S1 were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 95°C.

[0339] After reaching a reaction temperature of 95°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0340] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0341] After adding oxidizing solution O and reducing solution R, 6.27 g of ammonia solution (25% aqueous solution) was added to the reaction vessel over 5 minutes. Finally, 56.74 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0342] Comparative Example C6 :

[0343] The synthesis was carried out as follows: Emulsion A was prepared by mixing 39.73 g of emulsifier A, 24.72 g of emulsifier B, 18.54 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 12.36 g of acrylamide (50% aqueous solution), 5.81 g of allyl methacrylate, 728.00 g of methyl methacrylate, 486.74 g of n-butyl acrylate and 385.7 g of deionized water.

[0344] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0345] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0346] The reducing solution R was prepared by dissolving 1.47 g of acetone and sodium bisulfite in 9.66 g of deionized water.

[0347] 569.41 g of deionized water and 41.20 g of seed latex S1 were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 95°C.

[0348] After reaching a reaction temperature of 95°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0349] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0350] After adding oxidizing solution O and reducing solution R, 6.27 g of ammonia solution (25% aqueous solution) was added to the reaction vessel over 5 minutes. Finally, 55.77 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0351] Comparative Example C7 :

[0352] The synthesis was carried out as follows: Emulsion A was prepared by mixing 39.73 g of emulsifier A, 24.72 g of emulsifier B, 18.54 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 12.36 g of acrylamide (50% aqueous solution), 5.81 g of allyl methacrylate, 728.00 g of methyl methacrylate, 486.74 g of n-butyl acrylate and 385.7 g of deionized water.

[0353] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0354] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0355] The reducing solution R was prepared by dissolving 1.47 g of acetone and sodium bisulfite in 9.66 g of deionized water.

[0356] 569.41 g of deionized water and 41.20 g of seed latex S1 were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 85°C.

[0357] After reaching a reaction temperature of 85°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0358] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0359] After adding oxidizing solution O and reducing solution R, 6.27 g of ammonia solution (25% aqueous solution) was added to the reaction vessel over 5 minutes. Finally, 55.77 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0360] Comparative Example C8 :

[0361] The synthesis was carried out as follows: Emulsion A was prepared by mixing 44.14 g of emulsifier A, 24.72 g of emulsifier B, 1.18 g of 3-(trimethoxysilyl)propyl methacrylate, 18.54 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 12.36 g of acrylamide (50% aqueous solution), 5.81 g of allyl methacrylate, 687.89 g of methyl methacrylate, 605.27 g of n-butyl acrylate and 665.70 g of deionized water.

[0362] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0363] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0364] The reducing solution R was prepared by dissolving 1.47 g of acetone and sodium bisulfite in 9.66 g of deionized water.

[0365] 569.41 g of deionized water and 41.20 g of seed latex S1 were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 95°C.

[0366] After reaching a reaction temperature of 95°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0367] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0368] After adding oxidizing solution O and reducing solution R, 6.27 g of ammonia solution (25% aqueous solution) was added to the reaction vessel over 5 minutes. Finally, 55.77 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0369] Comparative Example C9 :

[0370] The synthesis was carried out as follows: Emulsion A was prepared by mixing 44.14 g of emulsifier A, 24.72 g of emulsifier B, 1.18 g of 3-(trimethoxysilyl)propyl methacrylate, 30.90 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 5.81 g of allyl methacrylate, 687.88 g of methyl methacrylate, 525.67 g of n-butyl acrylate and 665.62 g of deionized water.

[0371] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0372] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0373] The reducing solution R was prepared by dissolving 1.47 g of acetone and sodium bisulfite in 9.66 g of deionized water.

[0374] 569.41 g of deionized water and 41.20 g of seed latex S1 were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 95°C.

[0375] After reaching a reaction temperature of 95°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0376] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0377] After adding oxidizing solution O and reducing solution R, 6.27 g of ammonia solution (25% aqueous solution) was added to the reaction vessel over 5 minutes. Finally, 55.77 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0378] Comparative Example C10 :

[0379] The synthesis was carried out as follows: Emulsion A was prepared by mixing 59.59 g of emulsifier A, 37.08 g of emulsifier B, 36.83 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 10.09 g of 2-hydroxyethyl methacrylate, 6.21 g of acrylic acid, 739.99 g of methyl methacrylate, 461.49 g of n-butyl acrylate and 364.57 g of deionized water.

[0380] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0381] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0382] The reducing solution R was prepared by dissolving 1.47 g of sodium acetone-sodium bisulfite in 6.76 g of deionized water.

[0383] 551.01g of deionized water, 47.57g of seed latex S1, and 15.45g of sodium bicarbonate (6% aqueous solution) were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 85°C.

[0384] After reaching a reaction temperature of 85°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0385] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0386] After adding oxidizing solution O and reducing solution R, 62.00 g of sodium hydroxide solution (2% aqueous solution) was added to the reaction vessel over 37 minutes. Finally, the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0387] Comparative Example C11 :

[0388] The synthesis was carried out as follows: Emulsion A was prepared by mixing 33.11 g of emulsifier A, 20.60 g of emulsifier B, 37.08 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 9.89 g of 1,4-butanediol diacrylate, 703.90 g of methyl methacrylate, 503.67 g of n-butyl acrylate and 388.41 g of deionized water.

[0389] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0390] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0391] The reducing solution R was prepared by dissolving 1.47 g of sodium acetone-sodium bisulfite in 6.76 g of deionized water.

[0392] 556.19 g of deionized water and 71.16 g of seed latex S1 were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 85°C.

[0393] After reaching a reaction temperature of 85°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0394] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0395] After adding oxidizing solution O and reducing solution R, 31.00 g of sodium hydroxide solution (2% aqueous solution) was added to the reaction vessel over 37 minutes. Finally, 80.35 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0396] Comparative Example C12 :

[0397] The synthesis was carried out as follows: Emulsion A was prepared by mixing 66.21 g of emulsifier A, 41.20 g of emulsifier B, 37.08 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 9.89 g of 1,4-butanediol diacrylate, 6.18 g of tert-dodecyl mercaptan, 703.90 g of methyl methacrylate, 503.67 g of n-butyl acrylate and 388.41 g of deionized water.

[0398] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0399] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0400] The reducing solution R was prepared by dissolving 1.47 g of sodium acetone-sodium bisulfite in 6.76 g of deionized water.

[0401] 556.19 g of deionized water and 71.16 g of seed latex S1 were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 85°C.

[0402] After reaching a reaction temperature of 85°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0403] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0404] After adding oxidizing solution O and reducing solution R, 31.00 g of sodium hydroxide solution (2% aqueous solution) was added to the reaction vessel over 37 minutes. Finally, 80.35 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0405] Comparative Example C13: Embodiment 6 of the present invention from WO 2021 / 209543

[0406] The synthesis was carried out as follows: Emulsion A was prepared by mixing 10.21 g of emulsifier A, 6.33 g of emulsifier B, 3.76 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 4.12 g of acrylic acid, 8.48 g of itaconic acid, 3.17 g of tert-dodecyl mercaptan, 0.38 g of 3-(trimethoxysilyl)propyl methacrylate, 238.75 g of methyl methacrylate, 133.51 g of n-butyl acrylate and 214.30 g of deionized water.

[0407] Emulsion B was prepared by mixing 23.75 g of emulsifier A, 14.80 g of emulsifier B, 8.78 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 0.89 g of 3-(trimethoxysilyl)propyl methacrylate, 554.88 g of methyl methacrylate, 322.01 g of n-butyl acrylate, and 273.04 g of deionized water.

[0408] Initiator solution I was prepared by dissolving 3.83 g of sodium peroxide in 50.79 g of deionized water.

[0409] Oxidizing solution O was prepared by dissolving 1.26 g of tert-butyl hydroperoxide in 11.34 g of deionized water.

[0410] The reducing solution R was prepared by dissolving 1.15 g of sodium bisulfite in 7.68 g of deionized water.

[0411] 402.78g of deionized water and 19.69g of seed latex S1 were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 83°C.

[0412] After reaching a reaction temperature of 85°C, 30% by weight of initiator solution I and all of emulsion A are simultaneously fed into the reaction vessel over a period of 60 minutes. After the feeding of emulsion A is completed, the remaining 70% by weight of initiator solution I and all of emulsion B are simultaneously fed into the reaction vessel over a period of 140 minutes.

[0413] After the addition of emulsion B and initiator solution I is complete, the reaction vessel is stirred for another 20 minutes. Then, simultaneously but spatially separate feed vessels are used to feed oxidizing solution O and reducing solution R into the reaction vessel over a period of 60 minutes.

[0414] After adding oxidizing solution O and reducing solution R, 132.00 g of sodium hydroxide solution (5% aqueous solution) was added to the reaction vessel over 37 minutes. Finally, 80.35 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0415] Comparative Example C14 :

[0416] The synthesis was carried out as follows: Emulsion A was prepared by mixing 47.04 g of emulsifier A, 29.28 g of emulsifier B, 5.21 g of 3-(trimethoxysilyl)propyl methacrylate, 18.88 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 3.9 g of 2-hydroxypropyl methacrylate, 10.4 g of acrylamide, 5.2 g of itaconic acid, 754.05 g of methyl methacrylate, 517.00 g of n-butyl acrylate and 352.65 g of deionized water.

[0417] Initiator solution I was prepared by dissolving 4.80 g of sodium peroxide in 60.01 g of deionized water.

[0418] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0419] The reducing solution R was prepared by dissolving 1.47 g of acetone and sodium bisulfite in 9.66 g of deionized water.

[0420] 522.07 g of deionized water, 59.45 g of seed latex S1, and 11.02 g of sodium carbonate (6% aqueous solution) were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 85°C.

[0421] After reaching a reaction temperature of 85°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0422] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0423] After adding oxidizing solution O and reducing solution R, 100.00 g of sodium hydroxide solution (2% aqueous solution) was added to the reaction vessel over 37 minutes. Finally, 39.00 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0424] Comparative Example C15 :

[0425] The synthesis was carried out as follows: Emulsion A was prepared by mixing 47.04 g of emulsifier A, 29.28 g of emulsifier B, 18.88 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 18.00 g of acrylamide solution (50% aqueous solution), 5.2 g of itaconic acid, 4.94 g of 3-(trimethoxysilyl)propyl methacrylate, 750.14 g of methyl methacrylate, 520.91 g of n-butyl acrylate and 348.37 g of deionized water.

[0426] Initiator solution I was prepared by dissolving 4.50 g of sodium peroxide in 59.50 g of deionized water.

[0427] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0428] The reducing solution R was prepared by dissolving 1.47 g of sodium acetone-sodium bisulfite in 6.76 g of deionized water.

[0429] 522.70 g of deionized water, 59.45 g of seed latex S1, and 10.83 g of sodium carbonate (6% aqueous solution) were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 85°C.

[0430] After reaching a reaction temperature of 85°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0431] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0432] After adding oxidizing solution O and reducing solution R, 31.00 g of sodium hydroxide solution (2% aqueous solution) was added to the reaction vessel over 37 minutes. Finally, 37.00 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0433] Comparative Example C16 :

[0434] The synthesis was carried out as follows: Emulsion A was prepared by mixing 47.04 g of emulsifier A, 29.28 g of emulsifier B, 18.88 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 13.00 g of acrylamide solution (50% aqueous solution), 4.94 g of 3-(trimethoxysilyl)propyl methacrylate, 782.39 g of methyl methacrylate, 441.25 g of n-butyl acrylate and 389.80 g of deionized water.

[0435] Initiator solution I was prepared by dissolving 4.5 g of sodium peroxide in 59.50 g of deionized water.

[0436] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0437] The reducing solution R was prepared by dissolving 1.47 g of sodium acetone-sodium bisulfite in 6.76 g of deionized water.

[0438] 560.40 g of deionized water, 59.45 g of seed latex S1, and 10.83 g of sodium carbonate (6% aqueous solution) were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 85°C.

[0439] After reaching a reaction temperature of 85°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0440] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0441] After adding oxidizing solution O and reducing solution R, 31.00 g of sodium hydroxide solution (2% aqueous solution) was added to the reaction vessel over 37 minutes. Finally, 37.00 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0442] This invention I1 :

[0443] The synthesis was carried out as follows: Emulsion A was prepared by mixing 39.73 g of emulsifier A, 24.72 g of emulsifier B, 1.18 g of 3-(trimethoxysilyl)propyl methacrylate, 18.54 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 6.31 g of 2-hydroxyethyl methacrylate, 691.19 g of methyl methacrylate, 528.19 g of n-butyl acrylate and 673.43 g of deionized water.

[0444] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0445] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0446] The reducing solution R was prepared by dissolving 1.47 g of acetone and sodium bisulfite in 9.66 g of deionized water.

[0447] 556.19 g of deionized water and 41.20 g of seed latex S1 were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 95°C.

[0448] After reaching a reaction temperature of 95°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0449] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0450] After adding oxidizing solution O and reducing solution R, 3.00 g of ammonia solution (25% aqueous solution) was added to the reaction vessel over 5 minutes. Finally, 58.38 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0451] This invention I2 :

[0452] The synthesis was carried out as follows: Emulsion A was prepared by mixing 36.59 g of emulsifier A, 22.74 g of emulsifier B, 16.81 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 7.50 g of 2-hydroxyethyl methacrylate, 4.94 g of 3-(trimethoxysilyl)propyl methacrylate, 2.30 g of tert-dodecyl mercaptan, 736.74 g of methyl methacrylate, 478.55 g of n-butyl acrylate and 399.36 g of deionized water.

[0453] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0454] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0455] The reducing solution R was prepared by dissolving 1.47 g of sodium acetone-sodium bisulfite in 6.76 g of deionized water.

[0456] 542.09 g of deionized water, 67.08 g of seed latex S1, and 15.45 g of sodium bicarbonate (6% aqueous solution) were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 85°C.

[0457] After reaching a reaction temperature of 85°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0458] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0459] After adding oxidizing solution O and reducing solution R, 31.00 g of sodium hydroxide solution (2% aqueous solution) was added to the reaction vessel over 37 minutes. Finally, 27.00 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0460] This invention I3 :

[0461] The synthesis was carried out as follows: Emulsion A was prepared by mixing 33.77 g of emulsifier A, 21.01 g of emulsifier B, 17.95 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 9.75 g of 2-hydroxyethyl methacrylate, 4.94 g of 3-(trimethoxysilyl)propyl methacrylate, 2.77 g of tert-dodecyl mercaptan, 0.17 g of 1,4-butanediol diacrylate, 2.42 g of allyl methacrylate, 725.04 g of methyl methacrylate, 484.90 g of n-butyl acrylate, and 402.08 g of deionized water.

[0462] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0463] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0464] The reducing solution R was prepared by dissolving 1.47 g of sodium acetone-sodium bisulfite in 6.76 g of deionized water.

[0465] 542.09 g of deionized water, 67.08 g of seed latex S1, and 15.45 g of sodium bicarbonate (6% aqueous solution) were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 85°C.

[0466] After reaching a reaction temperature of 85°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0467] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0468] After adding oxidizing solution O and reducing solution R, 31.00 g of sodium hydroxide solution (2% aqueous solution) was added to the reaction vessel over 37 minutes. Finally, 27.00 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0469] This invention I4 :

[0470] The synthesis was carried out as follows: Emulsion A was prepared by mixing 33.11 g of emulsifier A, 20.60 g of emulsifier B, 12.36 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 8.27 g of 2-hydroxyethyl methacrylate, 3.71 g of 3-(trimethoxysilyl)propyl methacrylate, 2.25 g of tert-dodecyl mercaptan, 6.18 g of 1,4-butanediol diacrylate, 726.48 g of methyl methacrylate, 485.34 g of n-butyl acrylate, and 405.15 g of deionized water.

[0471] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0472] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0473] The reducing solution R was prepared by dissolving 1.47 g of sodium acetone-sodium bisulfite in 6.76 g of deionized water.

[0474] 554.35g of deionized water, 32.17g of seed latex S1, and 15.45g of sodium bicarbonate (6% aqueous solution) were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 85°C.

[0475] After reaching a reaction temperature of 85°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0476] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0477] After adding oxidizing solution O and reducing solution R, 31.00 g of sodium hydroxide solution (2% aqueous solution) was added to the reaction vessel over 37 minutes. Finally, 27.00 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0478] This invention I5 :

[0479] The synthesis was carried out as follows: Emulsion A was prepared by mixing 36.73 g of emulsifier A, 22.82 g of emulsifier B, 17.95 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 9.67 g of 2-hydroxyethyl methacrylate, 4.94 g of 3-(trimethoxysilyl)propyl methacrylate, 730.14 g of methyl methacrylate, 482.45 g of n-butyl acrylate and 396.51 g of deionized water.

[0480] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0481] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0482] The reducing solution R was prepared by dissolving 1.47 g of sodium acetone-sodium bisulfite in 6.76 g of deionized water.

[0483] 540.60 g of deionized water, 71.16 g of seed latex S1, and 15.45 g of sodium bicarbonate (6% aqueous solution) were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 85°C.

[0484] After reaching a reaction temperature of 85°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0485] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0486] After adding oxidizing solution O and reducing solution R, 31.00 g of sodium hydroxide solution (2% aqueous solution) was added to the reaction vessel over 37 minutes. Finally, 27.00 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0487] This invention I6 :

[0488] The synthesis was carried out as follows: Emulsion A was prepared by mixing 35.67 g of emulsifier A, 22.17 g of emulsifier B, 12.95 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 9.69 g of 2-hydroxyethyl methacrylate, 1.74 g of tert-dodecyl mercaptan, 4.92 g of 3-(trimethoxysilyl)propyl methacrylate, 726.00 g of methyl methacrylate, 489.11 g of n-butyl acrylate and 401.55 g of deionized water.

[0489] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0490] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0491] The reducing solution R was prepared by dissolving 1.47 g of sodium acetone-sodium bisulfite in 6.76 g of deionized water.

[0492] 540.94 g of deionized water, 70.23 g of seed latex S1, and 15.45 g of sodium bicarbonate (6% aqueous solution) were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 85°C.

[0493] After reaching a reaction temperature of 85°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0494] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0495] After adding the oxidizing solution O and the reducing solution R, 31.00 g of sodium hydroxide solution (2% aqueous solution) was added to the reaction vessel over 37 minutes. Finally, 27.00 g of deionized water was added, and the vessel was cooled to 25°C.

[0496] This invention I7 :

[0497] The synthesis was carried out as follows: Emulsion A was prepared by mixing 33.77 g of emulsifier A, 21.01 g of emulsifier B, 17.95 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 5 g of acrylamide (50% aqueous solution), 9.55 g of 2-hydroxyethyl methacrylate, 4.94 g of 3-(trimethoxysilyl)propyl methacrylate, 2.77 g of tert-dodecyl mercaptan, 1.2 g of allyl methacrylate, 725.04 g of methyl methacrylate, 484.90 g of n-butyl acrylate and 402.08 g of deionized water.

[0498] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0499] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0500] The reducing solution R was prepared by dissolving 1.47 g of sodium acetone-sodium bisulfite in 6.76 g of deionized water.

[0501] 542.09 g of deionized water, 67.08 g of seed latex S1, and 15.45 g of sodium bicarbonate (6% aqueous solution) were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 85°C.

[0502] After reaching a reaction temperature of 85°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0503] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0504] After adding oxidizing solution O and reducing solution R, 31.00 g of sodium hydroxide solution (2% aqueous solution) was added to the reaction vessel over 37 minutes. Finally, 27.00 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0505] This invention I8 :

[0506] The synthesis was carried out as follows: Emulsion A was prepared by mixing 33.77 g of emulsifier A, 21.01 g of emulsifier B, 17.95 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 9.55 g of 2-hydroxyethyl methacrylate, 4.94 g of 3-(trimethoxysilyl)propyl methacrylate, 2.77 g of tert-dodecyl mercaptan, 1.2 g of allyl methacrylate, 726.48 g of methyl methacrylate, 485.34 g of n-butyl acrylate and 402.08 g of deionized water.

[0507] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0508] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0509] The reducing solution R was prepared by dissolving 1.47 g of sodium acetone-sodium bisulfite in 6.76 g of deionized water.

[0510] 542.09 g of deionized water, 67.08 g of seed latex S1, and 15.45 g of sodium bicarbonate (6% aqueous solution) were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 85°C.

[0511] After reaching a reaction temperature of 85°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0512] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0513] After adding oxidizing solution O and reducing solution R, 31.00 g of sodium hydroxide solution (2% aqueous solution) was added to the reaction vessel over 37 minutes. Finally, 27.00 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0514] This invention I9 :

[0515] The synthesis was carried out as follows: Emulsion A was prepared by mixing 45.00 g of emulsifier A, 28.02 g of emulsifier B, 17.95 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 9.67 g of 2-hydroxyethyl methacrylate, 4.94 g of 3-(trimethoxysilyl)propyl methacrylate, 2.77 g of tert-dodecyl mercaptan, 1.20 g of allyl methacrylate, 725.04 g of methyl methacrylate, 484.20 g of n-butyl acrylate and 402.08 g of deionized water.

[0516] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0517] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0518] The reducing solution R was prepared by dissolving 1.47 g of sodium acetone-sodium bisulfite in 6.76 g of deionized water.

[0519] 542.09 g of deionized water, 60.15 g of seed latex S1, and 15.45 g of sodium bicarbonate (6% aqueous solution) were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 85°C.

[0520] After reaching a reaction temperature of 85°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0521] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0522] After adding oxidizing solution O and reducing solution R, 31.00 g of sodium hydroxide solution (2% aqueous solution) was added to the reaction vessel over 37 minutes. Finally, 27.00 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0523] This invention I10 :

[0524] The synthesis was carried out as follows: Emulsion A was prepared by mixing 45.03 g of emulsifier A, 27.99 g of emulsifier B, 17.95 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 9.69 g of 2-hydroxyethyl methacrylate, 4.92 g of 3-(trimethoxysilyl)propyl methacrylate, 2.77 g of tert-dodecyl mercaptan, 1.20 g of allyl methacrylate, 726.07 g of methyl methacrylate, 489.11 g of n-butyl acrylate and 402.08 g of deionized water.

[0525] Initiator solution I was prepared by dissolving 4.98 g of sodium peroxide in 42.50 g of deionized water.

[0526] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0527] The reducing solution R was prepared by dissolving 1.47 g of sodium acetone-sodium bisulfite in 6.76 g of deionized water.

[0528] 542.09 g of deionized water, 67.08 g of seed latex S1, and 15.45 g of sodium bicarbonate (6% aqueous solution) were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 85°C.

[0529] After reaching a reaction temperature of 85°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0530] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0531] After adding oxidizing solution O and reducing solution R, 31.00 g of sodium hydroxide solution (2% aqueous solution) was added to the reaction vessel over 37 minutes. Finally, 27.00 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0532] This invention I11 :

[0533] The synthesis was carried out as follows: Emulsion A was prepared by mixing 39.73 g of emulsifier A, 24.72 g of emulsifier B, 14.83 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 6.31 g of 2-hydroxyethyl methacrylate, 735.05 g of methyl methacrylate, 487.35 g of n-butyl acrylate and 452.32 g of deionized water.

[0534] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0535] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0536] The reducing solution R was prepared by dissolving 1.47 g of acetone and sodium bisulfite in 9.66 g of deionized water.

[0537] 569.41g of deionized water and 33.71g of seed latex S1 were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 85°C.

[0538] After reaching a reaction temperature of 85°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0539] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0540] After adding oxidizing solution O and reducing solution R, 2.00 g of ammonia solution (25% aqueous solution) was added to the reaction vessel over 5 minutes. Finally, 27.00 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0541] This invention I12 :

[0542] The synthesis was carried out as follows: Emulsion A was prepared by mixing 39.73 g of emulsifier A, 24.72 g of emulsifier B, 12.36 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 6.31 g of 2-hydroxyethyl methacrylate, 746.54 g of methyl methacrylate, 477.10 g of n-butyl acrylate and 393.00 g of deionized water.

[0543] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0544] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0545] The reducing solution R was prepared by dissolving 1.47 g of acetone and sodium bisulfite in 9.66 g of deionized water.

[0546] 569.41 g of deionized water, 33.71 g of seed latex S1, and 10.30 g of sodium carbonate (6% aqueous solution) were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 85°C.

[0547] After reaching a reaction temperature of 85°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0548] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0549] After adding oxidizing solution O and reducing solution R, 31.00 g of sodium hydroxide solution (2% aqueous solution) was added to the reaction vessel over 37 minutes. Finally, 35.00 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0550] This invention I13 :

[0551] The synthesis was carried out as follows: Emulsion A was prepared by mixing 39.73 g of emulsifier A, 30.90 g of emulsifier C, 12.36 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 6.31 g of 2-hydroxyethyl methacrylate, 746.54 g of methyl methacrylate, 477.10 g of n-butyl acrylate and 391.60 g of deionized water.

[0552] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0553] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0554] The reducing solution R was prepared by dissolving 1.47 g of acetone and sodium bisulfite in 9.66 g of deionized water.

[0555] 569.41 g of deionized water, 33.71 g of seed latex S1, and 10.30 g of sodium carbonate (6% aqueous solution) were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 85°C.

[0556] After reaching a reaction temperature of 85°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0557] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0558] After adding oxidizing solution O and reducing solution R, 31.00 g of sodium hydroxide solution (2% aqueous solution) was added to the reaction vessel over 37 minutes. Finally, 35.00 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0559] This invention I14 :

[0560] The synthesis was carried out as follows: Emulsion A was prepared by mixing 39.73 g of emulsifier A, 24.72 g of emulsifier B, 12.36 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 6.31 g of 2-hydroxyethyl methacrylate, 782.39 g of methyl methacrylate, 441.25 g of n-butyl acrylate and 393.00 g of deionized water.

[0561] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0562] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0563] The reducing solution R was prepared by dissolving 1.47 g of acetone and sodium bisulfite in 9.66 g of deionized water.

[0564] 569.41 g of deionized water, 33.71 g of seed latex S1, and 10.30 g of sodium carbonate (6% aqueous solution) were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 85°C.

[0565] After reaching a reaction temperature of 85°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0566] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0567] After adding oxidizing solution O and reducing solution R, 31.00 g of sodium hydroxide solution (2% aqueous solution) was added to the reaction vessel over 37 minutes. Finally, 35.00 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0568] This invention I15 :

[0569] The synthesis was carried out as follows: Emulsion A was prepared by mixing 39.73 g of emulsifier A, 24.72 g of emulsifier B, 12.36 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 6.31 g of 2-hydroxyethyl methacrylate, 846.66 g of methyl methacrylate, 376.98 g of 2-ethylhexyl acrylate, and 393.00 g of deionized water.

[0570] Initiator solution I was prepared by dissolving 3.19 g of sodium peroxide in 42.50 g of deionized water.

[0571] Oxidizing solution O was prepared by dissolving 1.22 g of tert-butyl hydroperoxide in 10.99 g of deionized water.

[0572] The reducing solution R was prepared by dissolving 1.47 g of acetone and sodium bisulfite in 9.66 g of deionized water.

[0573] 569.41 g of deionized water, 33.71 g of seed latex S1, and 10.30 g of sodium carbonate (6% aqueous solution) were added to a reaction vessel equipped with a stirrer and three separate feed lines, and the mixture was preheated to 85°C.

[0574] After reaching a reaction temperature of 85°C, 4.65 g of deionized water containing 0.35 g of sodium peroxide was added to the reaction vessel and stirred for 2 minutes. Then, emulsion A was fed into the reaction vessel over 150 minutes. Simultaneously, initiator solution I was fed into the reaction vessel from a spatially separate feed vessel, starting at the same time as emulsion A, over 150 minutes.

[0575] After the addition of emulsion A and initiator solution I is complete, the reaction vessel is stirred for another 30 minutes. Then, the reaction vessel is cooled to 75°C, and simultaneously, but spatially separate, oxidizing solution O and reducing solution R are fed into the reaction vessel over 60 minutes.

[0576] After adding oxidizing solution O and reducing solution R, 31.00 g of sodium hydroxide solution (2% aqueous solution) was added to the reaction vessel over 37 minutes. Finally, 35.00 g of deionized water was added, and the vessel was cooled to 25°C. The analytical data of the obtained dispersion are shown in Table 2: Experimental Analytical Data.

[0577] Table 1: Chemical properties (in pphm) of the comparative sample and the sample of the present invention

[0578]

[0579] Table 2: Analytical data of comparative examples and embodiments of the present invention

[0580]

[0581] Table 3: Application test results of samples from Table 2

[0582]

[0583] PVC 2 results. WU after re-drying

Claims

1. An aqueous polymer dispersion, said aqueous polymer dispersion being obtainable by free radical aqueous emulsion polymerization of an olefinically unsaturated monomer M, wherein said monomer M comprises a) A combination of the following substances, based on the total weight of monomer M, ranging from 0.5 wt% to 5.0 wt%. a1) At least one monomer Ma1, which is selected from C2-C6 (meth)acrylate hydroxyalkyl esters; a2) At least one monomer Ma2, selected from mono-olefinic unsaturated monosulfonic acids having 2 to 10 carbon atoms and their salts; b1) At least one monomer Mb1, based on 50% to 75.45% by weight of the total weight of monomer M, selected from nonionic monoolefinic unsaturated monomers having a solubility of up to 60 g / L in deionized water at 25 °C and 1 bar, and whose homopolymer has a glass transition temperature Tg of at least 50 °C. b2) At least one monomer Mb2, based on 24% to 49.45% by weight of the total weight of monomer M, selected from nonionic monoolefinic unsaturated monomers having a solubility of up to 60 g / L in deionized water at 25 °C and 1 bar, and whose homopolymer has a glass transition temperature Tg of up to 40 °C. c) Optional 0.05% to 2.0% by weight of at least one crosslinking monomer Mc; Furthermore, the aqueous polymer dispersion therefrom is substantially free of mono-olefinic unsaturated carboxylic acids, and the aqueous emulsion polymerization therefrom is optionally carried out in the presence of chain transfer compounds.

2. The aqueous polymer dispersion of claim 1, wherein the monomer M comprises, based on the total amount of monomer M, a combination of the following substances at 0.5% to 5% by weight, particularly 0.7% to 4.0% by weight. a1) at least one monomer Ma1, comprising 0.25% to 2.5% by weight of the total amount of monomer M; a2) At least one monomer Ma2, comprising 0.25% to 2.5% by weight of the total amount of monomer M.

3. The aqueous polymer dispersion according to any one of the preceding claims, wherein the monomer Ma1 is selected from C2-C6 (meth)acrylate hydroxyalkyl esters, preferably hydroxyethyl methacrylate, and the monomer Ma2 is 2-acrylamido-2-methylpropanesulfonic acid or its sodium salt.

4. The aqueous polymer dispersion according to any one of the preceding claims, wherein the monomer M comprises at least one crosslinking monomer Mc in an amount of 0.05% to 1.5% by weight, particularly 0.08% to 1.0% by weight, based on the total amount of monomer M.

5. The aqueous polymer dispersion according to any one of the preceding claims, wherein the crosslinking monomer Mc is selected from the group consisting of: polyene unsaturated monomers having at least two non-conjugated olefinic unsaturated double bonds and monoene unsaturated monomers having at least one additional functional group capable of reacting with itself.

6. The aqueous polymer dispersion according to any one of the preceding claims, wherein the monomer Mb1 is selected from the group consisting of: C1-C2-alkyl esters of methacrylate, tert-butyl acrylate, tert-butyl methacrylate, monovinyl aromatic monomers, and mixtures thereof.

7. The aqueous polymer dispersion according to any one of the preceding claims, wherein the monomer Mb2 is selected from the group consisting of: C1-C6 acrylic acid. 20 -Alkyl esters, excluding tert-butyl acrylate; C5-C of acrylic acid 20 -Cycloalkyl esters; C3-alkyl esters of methacrylate; n-butyl methacrylate; C5-C6 esters of methacrylate 20 -Alkyl ester; C8-C of methacrylic acid 20 Cycloalkyl esters and mixtures thereof.

8. The aqueous polymer dispersion according to any one of the preceding claims, wherein the aqueous emulsion polymerization is carried out in the presence of a chain transfer compound.

9. The aqueous polymer dispersion according to any one of the preceding claims, wherein the chain transfer compound has a thiol group.

10. The aqueous polymer dispersion according to any one of the preceding claims, wherein the amount of chain transfer compound is in the range of 0.05% to 1.2% by weight, particularly 0.1% to 0.9% by weight, based on the total amount of monomer M.

11. A method for preparing an aqueous polymer dispersion according to any one of the preceding claims, the method comprising the free radical aqueous emulsion polymerization of the monomer M, wherein the aqueous emulsion polymerization is preferably carried out in the presence of a chain transfer compound.

12. Use of the aqueous polymer dispersion according to any one of claims 1 to 10 as a binder or co-binder in aqueous coating compositions, particularly in architectural coating compositions and in coating compositions for molding mineral bodies.

13. A waterborne coating composition comprising a waterborne polymer dispersion according to any one of claims 1 to 10.

14. A method for producing a permanent coating on a surface, the method comprising: (a) Applying the coating composition according to claim 13 to the surface, and (b) Dry the coating composition to produce the permanent coating.

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