Aqueous polymer dispersions suitable as opacifiers in liquid formulations, manufacturing process and their use - Patents.com

Abstract

The present invention relates to an aqueous polymer dispersion suitable as an opacifier in liquid formulations, a manufacturing process, the use of such an aqueous polymer dispersion in a cleaning composition, and such a composition. The aqueous polymer dispersion can be obtained by radical emulsion polymerization in an aqueous environment by polymerizing i) at least one vinyl ester, ii) at least one (meth)acrylic acid ester (optionally containing methacrylic acid as a minor component, wherein the (meth)acrylic acid in the methacrylic acid ester is linked to a polyalkylene oxide derived block (PAO) via an ether functional group, the PAO consisting of 2 to 40 alkylene oxides (AOs), and iii) optionally further polymerizable monomers in the presence of a) a carboxyl group-containing compound selected from compounds having at least three carboxyl groups in their structure, at least 10 percent and at most 90 percent of which are deprotonated, b) at least one carboxylated or non-carboxylated sugar and / or carboxylated or non-carboxylated polysaccharide, and c) at least one emulsifier selected from nonionic and anionic surfactants. The resulting aqueous polymer dispersion optionally also contains sulfate and / or sulfite ions.

Description

[Technical Field]

[0001] The present invention relates to aqueous polymer dispersions suitable as opacifiers in liquid formulations.

[0002] The present invention further relates to an aqueous polymer dispersion obtainable by radical emulsion polymerization in an aqueous environment by polymerizing i) at least one vinyl ester, ii) at least one (meth)acrylic acid ester (which may optionally contain methacrylic acid as a minor component, wherein the (meth)acrylic acid in the methacrylic acid ester is linked via an ether functional group to a polyalkylene oxide derived block (PAO), the PAO consisting of 2 to 40 alkylene oxides (AOs)), and iii) optionally further polymerizable monomers, in the presence of a) a carboxyl group-containing compound selected from compounds having at least three carboxyl groups in its structure, at least 10 percent of which and at most 90 percent of which are deprotonated, b) at least one carboxylated or uncarboxylated sugar and / or carboxylated or uncarboxylated polysaccharide, and c) at least one emulsifier selected from nonionic and anionic surfactants. The resulting aqueous polymer dispersion optionally also contains sulfate and / or sulfite ions. The use of such aqueous polymer dispersions in cleaning compositions such as detergents is also encompassed, including the use of aqueous polymer dispersions as opacifiers.

[0003] The present invention also relates to formulations and compositions within the application areas of fabric and home care, industrial and institutional cleaning, comprising at least one aqueous polymer dispersion disclosed herein. [Background technology]

[0004] State-of-the-art opacifiers are based on styrene / methacrylic acid copolymers produced by emulsion polymerization. They are widely used in home care and personal care products. A drawback is the lack of biodegradability. Furthermore, current manufacturing processes suffer from reactor fouling and large amounts of coagulum, which reduces the overall capacity of commercial plants.

[0005] In D1 (EP 1924633, BASF), a process and dispersion consisting of vinyl acetate and 0.05-5.0 wt. % methacrylic acid obtained by free-radical initiated emulsion polymerization are claimed. Particle sizes were determined to be 100-200 nm. A protective colloid (Kollidon 30, polyvinylpyrrolidone K30) was used, and sodium dodecyl sulfate was used as an emulsifier. The target application is film coatings for sustained release of active ingredients in pharmacological and cosmetic applications. No biodegradation results were published. The use of polycarboxylates, such as carboxymethylcellulose, to improve biodegradability is not disclosed.

[0006] D2 (DE 102004031970, Wacker) describes a process and solution polymerization in methanol of vinyl monomers such as vinyl acetate and ethylenically unsaturated polyethers such as allyl polyethers. Esters of the corresponding polyethers with methacrylic acid having terminal groups OH and OR (where R can be an alkyl having C1 to C40) are also claimed. The target application is the production of plasticized vinyl acetate solid resins. No biodegradation results have been published. The use of polycarboxylates such as carboxymethyl cellulose to improve biodegradability is not disclosed.

[0007] In D3 (JP 2005089540, Konishi), an emulsion process is used to produce vinyl acetate polymer resins in the presence of polymerizable polyethylene glycol derivatives. The use of cellulose-based protective colloids is reported. Target applications include adhesive production, film formation, fiber and paper coatings, and binders in paper processing. No biodegradation results have been published. The use of polycarboxylates such as carboxymethyl cellulose to improve biodegradability is not disclosed.

[0008] In D4 (JP 06093007 A, Aica Kogyo, JP 1992-269400 A), a polyvinyl acetate-based emulsion was reported by emulsion polymerization of 50-100 wt. % vinyl acetate and 0-50 wt. % one or more comonomers (e.g., acrylic esters) using 10-200 wt. % water-soluble modified starch (e.g., esterified starch or etherified starch) as a protective colloid, based on the total monomers. The target application is the production of films with good low-temperature properties and high hardness. No biodegradation results were published. The use of polycarboxylates, such as carboxymethylcellulose, to improve biodegradability was not disclosed.

[0009] D5 (U.S. Pat. No. 4,708,999, Celanese, Air Products & Chemicals, U.S. Patent Application Publication No. 1986-894,419) describes the solution polymerization of vinyl acetate and C1-C12 alkyl polyethylene glycol methacrylate (polyethylene glycol with 25 ethylene oxide units) in methanol. The product is then methanolyzed. The amount of methacrylate is given in the examples as 0.56-1.85 mol %, and claim 1 includes 0.001-50 mol %. Molecular weights in the examples are given as 36,000-77,000 g / mol. Biodegradation results are not published. The use of polycarboxylates such as carboxymethylcellulose to improve biodegradability is not disclosed.

[0010] D6 (JP 59155411 A, Nippon Synthetic Chemical Industry, JP 1983-028686 A) describes a copolymer of an oxyalkylene group-containing unsaturated monomer and vinyl acetate in solution polymerization in alcohol. The copolymerization of vinyl acetate includes an oxyalkylene group-containing unsaturated monomer (such as methacrylic acid). The number of oxyalkylene groups, i.e., n, is advantageously 1 to 50, preferably about 3 to 50. The oxoalkylene group may terminate with an alkyl. Preferred examples include allyl polyoxoethylenes, one example being (10EO)-oxoethylene methacrylate. Modified vinyl acetate resins are water-soluble even in the absence of alkali metals and are suitable for use as pastes, adhesives, or aqueous solutions in paper processing, etc. No biodegradation results have been published. The use of polycarboxylates such as carboxymethyl cellulose to improve biodegradability is not disclosed.

[0011] D7 (U.S. Pat. No. 3,322,703, Cumberland Chemical) claims copolymers of vinyl acetate and an alkoxy polyalkylene glycol half ester of an unsaturated dicarboxylic acid, or / and vinyl acetate and an alkoxy polyalkylene glycol ester of an unsaturated monocarboxylic acid, and a method for preparing the same. Solution polymerization of vinyl acetate and methoxy polyethylene glycol maleate in methanol is given as an example. No applications are claimed, but they are described in the form of gummed articles that can be moistened to form a sticky film, for example, for postage stamps. No biodegradation results are published. The use of polycarboxylates, such as carboxymethylcellulose, to improve biodegradability is not disclosed.

[0012] Terpolymers consisting of vinyl alcohol, vinyl acetate and alkylpolyoxoethylene methacrylate esters are claimed in D8 (EP 199358 by Celanese Corp). Fabric protection comprises at least 50% vinyl alcohol in the terpolymer. Use of the terpolymer as a barrier layer in a thermoplastic process for packaging articles. No biodegradation results have been published. The use of polycarboxylates such as carboxymethyl cellulose to improve biodegradability is not disclosed. Summary of the Invention [Problem to be solved by the invention]

[0013] the purpose Due to climate change, one of the most important goals of the current detergent and cleaning (D&C) industry is to significantly reduce CO2 emissions per wash, for example, by improving cold water conditions by improving cleaning efficiency at low temperatures below 40, 30, or 20°C, or even lower, reducing the amount of chemicals used per wash, increasing the weight efficiency of cleaning technologies, and introducing bio-based ingredients. Therefore, one important goal of the D&C industry is the need for biodegradable ingredients to improve the sustainability of cleaning formulations, and in particular laundry and dishwashing formulations, and to avoid the accumulation of non-degradable compounds in ecosystems. Therefore, there is a need to provide compounds that are biodegradable but have at least the same performance as known but non-biodegradable compounds, where such biodegradability is measured within 28 days under specified conditions, as required by many users, especially in the detergent technology field, and as a future requirement by applicable legislation in several countries and regions around the world.

[0014] There is a high desire in the industry and by consumers to reduce such CO2 emissions or improve the "footprint" of any product, and there has been growing interest in terms of its origin, such as from natural or renewable resources, or in terms of its manufacture in relation to production efficiency and thus reduced energy usage, both compared to conventional products, in terms of its efficiency of use, such as same performance at lower amounts or higher performance at the same usage level, and even more so in terms of its persistence in the natural environment during and / or after its use, such as biodegradation.

[0015] As a result of these trends, there is a strong need for new biodegradable cleaning additives that provide at least equivalent cleaning properties and a reduced CO footprint by being bio-based, biodegradable, or even both. The materials should preferably exhibit good primary cleaning activity, soil removal against oily / greasy and particulate stains, and / or improve whiteness retention, thus also minimizing the amount of suspended and emulsified oily / greasy and particulate stains redeposited on fabrics or hard surfaces, etc.

[0016] It was therefore an object to provide opacifiers for compositions such as detergent, cleaning and / or fabric and home care compositions / formulations that have improved biodegradability. [Means for solving the problem]

[0017] This object has been solved by the aqueous dispersions defined herein, processes for producing such dispersions, and uses thereof, including compositions comprising such dispersions.

[0018] The aqueous dispersions of the present invention obtainable or obtained by the process according to the present invention may be used as opacifiers in certain compositions, such as detergent, cleaning and / or fabric and home care compositions / formulations. DETAILED DESCRIPTION OF THE INVENTION

[0019] definition All terms have their ordinary meanings unless otherwise defined within this disclosure, either below or throughout the specification.

[0020] Throughout this specification and the claims that follow, unless the context requires otherwise, the word "comprise" and variations such as "comprises" and "comprising" will be understood to imply the inclusion of a stated integer or step or group of integers or steps, but not the exclusion of any other integer or step or group of integers or steps. As used herein, the term "comprising" can be interchanged with the terms "containing" or "including," or, as sometimes used herein, with the term "having."

[0021] As used herein, "consisting of" excludes any element, step, or ingredient not specified in the claim element. As used herein, "consisting essentially of" does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim.

[0022] In each instance herein, any of the terms "comprising," "consisting essentially of," and "consisting of" may be replaced with either of the other two terms. "Comprising" may be replaced with "consisting essentially of" in preferred embodiments, and both may be replaced with "consisting of" in even more preferred embodiments.

[0023] The compositions of the present disclosure can "comprise" (i.e., contain other ingredients), "consist essentially of" (contain primarily or almost exclusively the ingredients mentioned, with other ingredients only in very small amounts, primarily as impurities), or "consist of" (i.e., contain only the ingredients mentioned, plus possibly and preferably only impurities unavoidable in the technical circumstances).

[0024] Similarly, the terms "substantially free of..." or "substantially free from..." or "(containing / comprising) essentially no..." may be used herein; this means that the indicated material is at the very minimum not intentionally added to the composition to form part of it, or preferably is not present at analytically detectable levels. It is meant to encompass compositions in which the indicated material is present only as an impurity in one of the other intentionally included materials. The indicated material may be present, if at all, at a level of less than 1%, or even less than 0.1%, or even less than 0.01%, or even 0% by weight of the composition.

[0025] Generally, as used herein, the term "obtainable by" does not necessarily mean that the corresponding product has been produced (i.e., obtained) by the corresponding method or process described in each specific context, but includes a product that exhibits all the characteristics of a product that would be produced (obtained) by said corresponding method or process, even if said product was not actually produced (obtained) by such a method or process. However, the term "obtainable by" also encompasses the more restrictive term "obtained by," i.e., includes a product that has actually been produced (obtained) by the corresponding method or process described in each specific context.

[0026] When any definition used herein requires that a compound or a substituent of a compound consist of "at least a certain number of carbon atoms," the number of carbon atoms refers to the total number of carbon atoms in the compound or the substituent of the compound. For example, in the case of a substituent disclosed as "an alkyl ether having at least 8 carbon atoms containing an alkylene oxide group," the total number of at least 8 carbon atoms must be the sum of the number of carbon atoms in the alkyl portion and the number of carbon atoms in the alkylene oxide portion.

[0027] All such terms not specifically defined have their ordinary meanings known in the art of organic chemistry.

[0028] As used herein, the articles "a" and "an," when used in a claim or an embodiment, are understood to mean one or more of what is claimed or described. As used herein, the terms "include" and "including" are meant to be open-ended and thus encompass more than the specific items recited following the word.

[0029] The term "about," as used herein, encompasses both the exact numerical value "X," as referred to, for example, as "about X%," and small variations of X, including variations of minus 5 to plus 5%, preferably minus 2 to plus 2%, more preferably minus 1 to plus 1%, and even more preferably minus 0.5 to plus 0.5%, and smaller, from X (setting X as 100% for this calculation). Of course, in cases where a given numerical value X is itself already "100%" (e.g., purity), the term "about" can clearly mean deviations less than "100," and therefore only definitively means deviations less than "100."

[0030] The term "water-free" means that the composition contains 5% or less by weight of water based on the total amount of solvent, in another embodiment 1% or less by weight of water based on the total amount of solvent, and in a further embodiment the solvent contains no water at all.

[0031] All temperatures herein are in degrees Celsius (°C) unless otherwise indicated. All measurements herein are made at 20°C and at atmospheric pressure unless otherwise specified. In all embodiments of the present disclosure, all percentages are by weight of the total composition unless otherwise specified. All ratios are by weight unless otherwise specified.

[0032] The phrase "fabric care composition" is meant to include compositions and formulations designed to treat fabrics. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric cleaning compositions, laundry pre-wash agents, laundry pre-treatment agents, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, washing additives, post-rinse fabric treatment agents, ironing aids, unit dose formulations, delayed delivery formulations, detergents contained on or in porous substrates or nonwoven sheets, and other suitable forms that may be apparent to those skilled in the art in light of the teachings herein and the detailed description herein below. Such compositions may be used as laundry pre-treatment agents, laundry post-treatment agents, or may be added during the rinse or wash cycle of a laundry operation, and as further detailed herein below when describing the uses and applications of the compositions of the present invention and those comprising such inventive dispersions.

[0033] The molecular weight descriptors Mw, Mn and molecular weight polydispersity (polydispersity index PDI); pH value. All percentages given are weight percentages based on the total weight of the composition, dispersion, feedstock, mixture, etc., unless otherwise specified; abbreviated as "wt. %."

[0034] "Biodegradable", "biodegradation", with or without the addition "tested under standard conditions", means biodegradation, and where a percentage such as "30% biodegradation / biodegradable" of a mentioned substance, compound or formulation is given, this has been determined using a biodegradation test in accordance with OECD 301F (used in the Examples section).

[0035] "Mean particle size" and corresponding "mean particle size measurement" refer to particle size D[4,3] measured using a Malvern Mastersizer 2000 in an aqueous environment using standard methods and components. The Mastersizer used in connection with the present invention was equipped with a Hydro 2000S(a) accessory and used water as the dispersant at a concentration of 0.0220 volume percent.

[0036] By "532 nm wavelength light" transmittance is meant the transmittance measured at a wavelength of 532 nm light using a standard instrument, preferably a Hach Lange DR6000 spectrometer, in a 1 centimeter long cuvette of dispersion at a concentration of 0.01% by weight and through which the light beam passes, and compared to the transmittance of a standard material (usually pure, preferably distilled or even bidistilled water, suitable for such measurements).

[0037] pH measurements are performed as described in the experimental section.

[0038] Throughout this specification, the term "compound of the invention" may be used instead of "(aqueous) dispersion of the invention" and "(aqueous) dispersion of this (present) invention", meaning that the compound is disclosed herein as the invention, is defined by its structure and / or its manufacturing process, and / or can be obtained by the process defined herein.

[0039] The definitions given in the "Definitions" section above and their preferences are included as part of the present invention as set forth herein below.

[0040] The specific embodiments described throughout this disclosure are included herein as part of the present invention, and various additional options disclosed herein as "optional," "preferred," "more preferred," "even more preferred," or "most preferred" (or "preferably," etc.) options for a particular embodiment may be individually and independently selected (provided that such independent selection is possible due to the nature of the feature or such independent selection is not expressly excluded) and then combined in any of the other embodiments (where other such options and preferences may also be individually and independently selected, but only if such independent selection is not possible due to the nature of the feature or such independent selection is expressly excluded), with all such possible combinations being included as part of the present invention as separate embodiments.

[0041] Specifically, the present invention provides the following: a) an ethylenically unsaturated monomer M, (1) (M1) at least one vinyl ester, preferably comprising vinyl acetate, more preferably comprising at least 50%, even more preferably at least 90% vinyl acetate; and (2) (M2) at least one (meth)acrylic acid ester, optionally containing methacrylic acid as a minor component, in which the (meth)acrylic acid in the methacrylic acid ester is linked via an ether functional group to a polyalkylene oxide derived block (PAO), the PAO consisting of 2 to 40 alkylene oxide (AO), most preferably 25 AO-units, the PAO preferably being linked via the ether functional group to a C1 to C24, preferably at least C4, more preferably at least C6, even more preferably C8 to C24-aliphatic alkanol, Most preferably further bonded to a C18-aliphatic alkanol, AO preferably selected from EO, PO and / or BuO, more preferably at least EO in an amount of from 50% by weight, more preferably at least 75% by weight, even more preferably at least 90% by weight, most preferably essentially EO, based on the total AO; preferably containing methacrylic acid, more preferably methacrylic acid ester and free methacrylic acid in a ratio of about 70% by weight / 30% to 80% by weight / 20% by weight, more preferably about 75% by weight / 25% by weight; (3) (M3) Optional further monomer (preferably absent) polymerizable with M1 and M2 an ethylenically unsaturated monomer M, comprising: b) 1 to 15% by weight, preferably 2 to 10% by weight, more preferably 3 to 8% by weight, and most preferably 4 to 6% by weight, based on the total weight of the (CGCC) monomer M, of a carboxyl group-containing compound selected from compounds having at least 3, more preferably at least 6, 8, 10, 15, 20, 25 or more carboxyl groups in their structure, with at least 10 percent and up to 90 percent of the carboxyl groups being deprotonated (and thus forming salts with counterions selected from Na, K, NH4, Mg, Ca), and selected from citric acid, isocitric acid; ethylenediaminetetraacetic acid; nitriloacetic acid; tartaric acid; oligomeric and polyacrylic acids; oligomeric and polymethacrylic acids; trimellitic acid; oligomeric amino acids containing carboxyl groups, such as polyaspartic acid; oligomeric and polyglutamic acid; carboxylic acid; oligomers and polyacetates having carboxy groups, such as poly(glyoxylic)aldehyde; carboxylated oligomeric and polymeric sugars, such as oxidized starch (a mixture of amylopectin and amylose); polyglucronates; cellulose oxidized to celluronate; natural polycarboxylic polysaccharides, such as xylan; pectinic acid; alginic acid; carboxymethylated polysaccharides based on 1,4-polyglucan, 1,3-polyglucan, and 1,6-polyglucan; polyuronic acids based on 1,4-polyglucan, 1,3-polyglucan, and 1,6-polyglucan; polygalacturons; carboxyl group-containing compounds, preferably selected from the group including carboxylated polysaccharides, more preferably carboxylated cellulose, and even more preferably carboxylated methylcellulose (carboxymethylcellulose, "CMC"); and c) (S) at least one (non-carboxylated) sugar and / or polysaccharide, such as glucose, starch degradation products, maltodextrin, in an amount of 2 to 50% by weight, preferably 5 to 35% by weight, more preferably 10 to 30% by weight, most preferably 15 to 25% by weight, based on the total weight of the monomer M, and d) at least one emulsifier selected from nonionic and anionic surfactants, i) at least one nonionic surfactant, anionic emulsifiers having at least one anionic group selected from phosphate, phosphonate, sulfate and sulfonate groups; anionic emulsifiers, typically used in the form of their alkali metal salts, in particular their sodium salts, or in the form of their ammonium salts; Preferably, anionic emulsifiers have at least one sulfate or sulfonate group or at least one phosphate or phosphonate group, more preferably at least one sulfonate or sulfate group, and most preferably only one sulfonate or sulfate group. is selected from i)a) the anionic emulsifier having at least one sulfate or sulfonate group is preferably - salts of alkyl sulfates, in particular C8 to C22 alkyl sulfates, in particular alkali metal and ammonium salts, - the salts, in particular the alkali metal and ammonium salts, of sulfuric acid monoesters of C2-C3 alkoxylated alkanols, in particular of sulfuric acid monoesters of C2-C3 alkoxylated C8-C22 alkanols, preferably having a C2-C3 alkoxylation level (AO level) ranging from 2 to 40, - sulfuric acid monoesters of C2-C3 alkoxylated alkylphenols, in particular the salts of sulfuric acid monoesters of C2-C3 alkoxylated C4-C18-alkylphenols, in particular the alkali metal and ammonium salts (AO level preferably 3-40), - salts, in particular alkali metal and ammonium salts, of alkylsulfonic acids, in particular C8-C22-alkylsulfonic acids; - salts, especially alkali metal and ammonium salts, of dialkyl esters, in particular di-C4-C18-alkyl esters of sulfosuccinic acid, - salts, in particular alkali metal and ammonium salts, of alkylbenzenesulfonic acids, in particular C4 to C22 alkylbenzenesulfonic acids, and - salts, especially alkali metal and ammonium salts, of mono- or disulfonated alkyl-substituted diphenyl ethers, for example bis(phenylsulfonic acid) ethers having a C4-C24 alkyl group on one or both aromatic rings; (The term "C2-C3 alkoxylated" means that the compound is ethoxylated, propoxylated or coethoxylated / propoxylated, i.e., that the compound is obtained by a process that introduces polyethylene oxide, polypropylene oxide or poly(ethylene oxide-co-propylene oxide) groups, respectively.) Selected from; i) b) The anionic emulsifier having at least one phosphate or phosphonate group is preferably salts, especially alkali metal and ammonium salts, of mono- and dialkyl phosphates, in particular C8-C22-alkyl phosphates, - phosphoric acid monoesters of C2-C3-alkoxylated alkanols, preferably having an alkoxylation level in the range from 2 to 40, in particular from 3 to 30, such as phosphoric acid monoesters of ethoxylated C8-C22 alkanols, preferably having an ethoxylation level (EO level) in the range from 2 to 40, phosphoric acid monoesters of propoxylated C8-C22 alkanols, preferably having a propoxylation level (PO level) in the range from 2 to 40, and salts, in particular alkali metal and ammonium salts, of phosphoric acid monoesters of ethoxylated-co-propoxylated C8-C22 alkanols, preferably having an ethoxylation level (EO level) in the range from 1 to 20 and a propoxylation level of 1 to 20, salts of phosphoric acid monoesters of C2-C3-alkoxylated alkylphenols, in particular salts of phosphoric acid monoesters of C2-C3-alkoxylated C4-C18-alkylphenols, in particular alkali metal and ammonium salts (AO level preferably 3-40); salts, in particular alkali metal and ammonium salts, of alkylphosphonic acids, in particular C8-C22-alkylphosphonic acids, and - salts of alkylbenzenephosphonic acids, in particular C4-C22-alkylbenzenephosphonic acids, in particular alkali metal and ammonium salts Selected from; More preferred anionic emulsifiers are those from the following group: - salts of alkyl sulfates, in particular C8 to C22 alkyl sulfates, in particular alkali metal and ammonium salts, the salts, especially alkali metal salts, of sulfuric acid monoesters of C2-C3-alkoxylated alkanols, in particular of sulfuric acid monoesters of C2-C3-alkoxylated C8-C22-alkanols, preferably having an AO level in the range from 2 to 40; - sulfuric acid monoesters of C2-C3-alkoxylated alkylphenols, in particular those of C2-C3-alkoxylated C4-C18-alkylphenols (AO level preferably 3-40); alkylbenzenesulfonic acids, in particular C4-C22 alkylbenzenesulfonic acids, and - For example, mono- or disulfonated alkyl-substituted diphenyl ethers of bis(phenylsulfonic acid) ethers having a C4-C24 alkyl group on one or both aromatic rings. Selected from; ii) at least one nonionic surfactant for example, - C2-C3-alkoxylated mono-, di- and trialkylphenols, the number of repeating units of which in the alkylene oxide derived moiety is preferably 3 to 50 and / or the alkyl groups are preferably C4-C10-alkyl; - C2-C3 alkyloxates of long-chain alcohols, such as ethoxylates, propoxylates or ethoxylate-co-propoxylates, in which the number of repeating units of the alkylene oxide-derived moiety is preferably 3 to 100 and / or the alkyl group is preferably C8 to C36-alkyl, and polyethylene oxide / polypropylene oxide homo- and copolymers, which may contain alkylene oxide units copolymerized in random distribution or in the form of blocks or mixtures of homoblocks and random blocks; More preferred are those in which the alkyl group C8 to C30 has an average alkoxylation level of 5 to 100, and particularly preferred among these are those having a linear C12 to C20 alkyl group and an average alkoxylation level of 10 to 50, C2 to C3-alkoxylated monoalkylphenols, and C2 to C3-alkoxylated long-chain alkanols. an emulsifier selected from aromatic aliphatic or aliphatic nonionic emulsifiers selected from: and e) optionally sulfate ions, and f) optionally sulfite ions and preferably the amount of M1 is between 80 and 99.99 mol %, more preferably the amount of M1 is at least 98% and the amount of M2 is 0.001 to 20 mol %, more preferably 0.1, even more preferably 0.2, even more preferably 0.5, most preferably 0.7, preferably at most 10, even more preferably at most 5, more preferably at most 2%, most preferably the amount of M1 is about 99% by weight, the amount of M2 is about 1% by weight, and the total amount of M1+M2 is 100% by weight; and The dispersion relates to an aqueous polymer dispersion having, after completion of polymerization, a pH of at most 4, more preferably less than 4, even more preferably at most 3.8, even more preferably at most 3.6, more preferably at least 2.5, even more preferably at least 3, even more preferably at least 3.2, and most preferably at least 3.4.

[0042] In a preferred embodiment 2 of the aqueous polymer dispersion defined above, the (M1) vinyl ester monomer comprises at least 50%, even more preferably at least 90%, of vinyl acetate, based on the total molar amount of vinyl esters.

[0043] In another preferred embodiment 3, (M2) at least one (meth)acrylic acid ester is (meth)acrylic acid linked to a polyalkylene oxide derived block (PAO) via an ether functional group, wherein the PAO comprises 20 to 30 alkylene oxides (AO), most preferably 25 AO units, and the PAO is preferably further linked to a C14 to C22 aliphatic alkanol, most preferably a C16 / 18 aliphatic alkanol, via an ether functional group, wherein the AO is selected from EO and PO and / or BuO, more preferably EO and PO, wherein the EO is in an amount of from 75% by weight, more preferably at least 90% by weight, based on the total AO, most preferably essentially EO only; and further comprising methacrylic acid, wherein the methacrylic acid ester and free methacrylic acid are in a ratio of about 70% by weight / 30% to 80% by weight / 20% by weight, more preferably about 75% by weight / 25% by weight.

[0044] In a further preferred embodiment 4, (M3) is not included.

[0045] In an even more preferred embodiment 5, in the aqueous polymer dispersion defined above, the (M1) vinyl ester monomer comprises at least 50%, even more preferably at least 90%, of vinyl acetate, based on the total molar amount of vinyl esters; (M2) at least one (meth)acrylic acid ester is (meth)acrylic acid linked via an ether functional group to a polyalkylene oxide derived block (PAO), the PAO consisting of 20 to 30 alkylene oxides (AO), most preferably 25 AO units, the PAO being preferably further linked via an ether functional group to a C14 to C22 aliphatic alkanol, most preferably a C16 / 18 aliphatic alkanol, the AO being selected from EO and PO and / or BuO, more preferably EO and PO, the EO being in an amount of from 75% by weight, more preferably at least 90% by weight, based on the total AO, most preferably essentially EO only; and further comprising methacrylic acid, the methacrylic acid ester and free methacrylic acid being in a ratio of about 70% by weight / 30% to 80% by weight / 20% by weight, more preferably about 75% by weight / 25% by weight, and excluding (M3).

[0046] In an even more preferred embodiment 6, (M1) the vinyl ester monomer comprises at least 90% vinyl acetate, preferably essentially only vinyl acetate, based on the total molar amount of vinyl esters; (M2) at least one (meth)acrylic acid ester is (meth)acrylic acid linked via an ether functionality to a polyalkylene oxide derived block (PAO), wherein the PAO comprises 23 to 27 alkylene oxides (AO), most preferably an average of 25 AO units, and the PAO is preferably further linked via an ether functionality to a C16 / 18-aliphatic alkanol, most preferably a C16 / 18-aliphatic alkanol, wherein the AO is essentially only EO; and further comprises methacrylic acid, wherein the methacrylic acid ester and free methacrylic acid are in a ratio of about 70% / 30% to 80% / 20% by weight, more preferably about 75% / 25% by weight; and (M3) is absent.

[0047] In a further more preferred embodiment 7 of the aqueous polymer dispersion defined above, (M1) is vinyl acetate, (M2) at least one (meth)acrylic acid ester is methacrylic acid bonded to a polyethylene oxide block (PEO) via an ether functional group, the PEO consisting of an average of 25 AO units, the PEO further bonded to a C16 / 18-aliphatic alkanol via an ether functional group and further comprising methacrylic acid, the methacrylic acid ester and free methacrylic acid being in a ratio of about 75% by weight / 25% by weight, and (M3) is absent.

[0048] In a further preferred embodiment 8, preferably in combination with any of the above embodiments, the aqueous dispersion comprises as (CGCC) a carboxyl group-containing compound selected from carboxylated polysaccharides, more preferably carboxylated cellulose, even more preferably carboxylated methyl cellulose (carboxymethyl cellulose, "CMC"), preferably in an amount of 1 wt. % to a maximum of 15 wt. %, more preferably a maximum of 10 wt. %, even more preferably a maximum of 5 wt. %, most preferably about 5 wt. %, based on the total amount of monomers (M1+M2+M3).

[0049] It is believed that CGCC can interact with the polymerized moieties derived from at least one monomer M2 in the polymer product dispersed in the dispersion. Such interaction appears to provide excellent compatibility and stability of the dispersion; it also favors attack on the chemical structure, thus resulting in the observed high biodegradation rate of the aqueous polymer dispersion, which is higher than that of the dispersion without the carboxyl group-containing compound (CGCC).

[0050] In one further preferred embodiment 9, preferably in combination with any of the above embodiments, the aqueous polymer dispersion comprises at least one sugar and / or polysaccharide that is an (S) starch degradation product, preferably maltodextrin, in an amount of 10 to 30 wt. %, most preferably 15 to 25 wt. %, based on the total weight of monomers M.

[0051] In a preferred variation of this embodiment 9 above, (S) is a degraded starch having a dextrose equivalent according to Lane and Eynon in the range of 2-40%.

[0052] In preferred variants of the two above embodiments, (S) is a maltodextrin with a DE value of 10-30, preferably 12-16 or 25-30.

[0053] In preferred variants of the above two embodiments 8 and 9, (S) is a degraded starch having a number average molecular weight, determined by osmometry, in the range of 300 to 2000 daltons, preferably in the range of 5 to 150, more preferably up to 70, even more preferably up to 50, more preferably from 10, even more preferably from 15, and most preferably from 20, in weight percent based on the total weight of monomers M1+M2+M3, respectively.

[0054] Such degraded starches can be obtained by known means such as chemical degradation, catalytic degradation with suitable catalysts or using enzymes, etc. In this specification, (S) is preferably derived from enzymatic degradation, as this is a clean and fast approach with essentially no chemical residues from the degradation reaction in the degradation products (other than starch and sugars derived from starch).

[0055] Additionally, the use of maltodextrin provides increased stability at lower storage temperatures for the dispersions of the present invention.

[0056] The aqueous polymer dispersions of the present invention can be obtained with D[4,3] values ​​determined by static light scattering of at least 400 and up to 1000 nm. Therefore, such dispersions are suitable as opacifiers in liquid formulations. Their use as opacifiers is also claimed herein.

[0057] The inventive aqueous polymer dispersion of any of the embodiments disclosed herein has at least one, preferably at least two, more preferably at least three, and most preferably all of the following properties a) to d) defined herein below: a) a transmittance of 532 nm wavelength light of at least 20% when measured as a 0.01% by weight dispersion in water; b) a pH of 2.5 to 9, preferably from 3, more preferably from 3.3, and more preferably up to 7, even more preferably up to 6, even more preferably up to 5, most preferably about 3.5; c) a density of 1.04 to 1.08 g / mL measured as a 10 wt% dispersion (solids basis), and d) Viscosity of 30 to 1000 mPas (Brookfield viscosity, spindle 3; measured as a 30 wt. % dispersion containing 30 wt. % active substance (active substance = polymer + CGCC + S); based on solids; concentration applicable by measurement).

[0058] Also part of the present invention is a process suitable for large scale production of the inventive aqueous polymer dispersions of any of the embodiments disclosed herein, such process comprising: (A) an ethylenically unsaturated monomer M, (M1) at least one vinyl ester, preferably comprising vinyl acetate, more preferably comprising at least 50%, even more preferably at least 90% vinyl acetate, and (M2) at least one (meth)acrylic acid ester, optionally containing methacrylic acid as a minor component, in which the (meth)acrylic acid in the methacrylic acid ester is linked via an ether functional group to a polyalkylene oxide derived block (PAO), the PAO consisting of 2 to 40 alkylene oxides (AO), most preferably 25 AO-units, the PAO preferably being linked via the ether functional group to a C1 to C24, preferably at least C4, more preferably at least C6, even more preferably C8 to C24-aliphatic alkanol, most preferably Preferably further bound to a C18-aliphatic alkanol, AO preferably selected from EO, PO and / or BuO, more preferably at least EO in an amount of from 50% by weight, more preferably at least 75% by weight, even more preferably at least 90% by weight, most preferably essentially EO, based on the total AO; preferably containing methacrylic acid, more preferably methacrylic acid ester and free methacrylic acid in a ratio of about 70% by weight / 30% to 80% by weight / 20% by weight, more preferably about 75% by weight / 25% by weight; (M3) Optional further monomers (preferably absent) that are polymerizable with M1 and M2 an ethylenically unsaturated monomer M comprising: at least one emulsifier, - water, - 1 to 15% by weight, preferably 2 to 10% by weight, more preferably 3 to 8% by weight, and most preferably 4 to 6% by weight, based on the total weight of the (CGCC) monomer M, of carboxyl group-containing compounds selected from compounds having at least 3, more preferably at least 6, 8, 10, 15, 20, 25, etc. carboxyl groups in their structure, in which at least 10 percent and at most 90 percent of the carboxyl groups are deprotonated (and thus form salts with counterions selected from Na, K, NH4, Mg, Ca), and which are selected from citric acid, isocitric acid; ethylenediaminetetraacetic acid; nitriloacetic acid; tartaric acid; oligomeric and polyacrylic acids; oligomeric and polymethacrylic acids; trimellitic acid; oligomeric amino acids containing carboxy groups, such as polyaspartic acid; oligomeric and polyglutamic acid; carboxylated oligomeric and polymeric sugars such as oxidized starch (a mixture of amylopectin and amylose); polyglucuronates; cellulose oxidized to celluronate; natural polycarboxylic polysaccharides such as xylan; pectinic acid; alginic acid; carboxymethylated polysaccharides based on 1,4-polyglucan, 1,3-polyglucan, and 1,6-polyglucan; polyuronic acids based on 1,4-polyglucan, 1,3-polyglucan, and 1,6-polyglucan; polygalacturons; carboxyl-containing compounds, preferably selected from the group including carboxylated polysaccharides, more preferably carboxylated cellulose, and even more preferably carboxylated methylcellulose (carboxymethylcellulose, "CMC"); and (S) at least one (non-carboxylated) sugar and / or polysaccharide, such as glucose, starch degradation products, maltodextrin, in an amount of 2 to 50% by weight, preferably 5 to 35% by weight, more preferably 10 to 30% by weight, most preferably 15 to 25% by weight, based on the total weight of the monomers M; In the presence of polymerizing using at least one radical initiator, or preferably a radical initiator pair comprising a peroxide and a reducing compound; Such polymerization is - in a reaction vessel equipped with either a pressurizing device and / or a device for controlling the boiling of the components, by which means the components can be contained in the reaction vessel during reaction at high temperature; - at a temperature of 60-90, preferably 70-80 ° C; at a pH of at most 4, more preferably below 4, even more preferably at most 3.8, even more preferably at most 3.6 the steps to be performed; Furthermore B) optionally adding additional radical initiator or initiator couple to further reduce the content of unreacted monomer and / or reduce the color of the resulting polymer dispersion; C) optionally adding at least one further reducing compound to reduce the color of the resulting polymer dispersion; D) optionally adding at least one further additive that may be required or desired as an additional component into the resulting polymer dispersion; E) optionally carrying out a step of removing volatilizable compounds from the reaction mixture by using a distillation step and / or a stripping step using steam or gas, preferably steam; F) optionally filtering the polymer dispersion from the previous step, preferably using a 125 micrometer filter; to obtain an aqueous polymer dispersion.

[0059] As a result of the polymerization reaction, the aqueous dispersion may contain sulfites and / or sulfates, which arise primarily from the use of persulfate initiators.

[0060] During polymerization, the pH of the mixture typically decreases due to the formation of acid from the use of persulfate initiators. In principle, this decrease in pH can be minimized by adding a base. However, the use of a base is not preferred. As more base is added, the amount of electrolyte increases, and the amount of coagulation typically increases.

[0061] In a preferred embodiment P1 of the process defined above, for the main polymerization step at least one persulfate and ascorbic acid and / or isoascorbic acid are used as radical polymerization initiators.

[0062] In a preferred embodiment P2 of the process defined above, preferably in combination with any of the embodiments defined above, the radical polymerization initiator additionally comprises a transition metal, preferably an iron-containing salt. In the most preferred embodiment P2a, no transition metal is used. The iron-containing salt is typically a complex of an iron cation, such as a complex with EDTA. Such complexes are known for such use in combination with persulfate radical initiators.

[0063] In a preferred embodiment P3 of the process defined above, preferably in combination with any of the embodiments defined above, at least one hydroperoxide and at least one sulfite salt are used in the post-polymerization step.

[0064] In a preferred embodiment P3 of the process defined above, preferably in combination with any of the above embodiments, at least 5% of the total amount of hydroperoxide added in the post-polymerization step is added after the end of the addition of sulfite.

[0065] In a preferred embodiment P4 of the process defined above, preferably in combination with any of the embodiments defined above, volatile components are removed using steam distillation, thermal distillation, vacuum distillation, gas stripping to reduce, preferably essentially remove, the residual amounts of monomers M1 and reaction by-products to a level required or acceptable for the intended area of ​​application, such step being carried out at ambient, reduced or elevated pressure (maximum 2 bar absolute) to reduce the content of residual volatile monomers such as organic solvents, vinyl esters, etc. to a content of at most 1 weight percent, preferably at most 0.5, more preferably at most 0.01%, based on the total weight of the polymer dispersion obtained.

[0066] In a preferred embodiment P5 of the process defined above, preferably in combination with any of the embodiments defined above, the dispersion finally obtained after the last process step for polymerization and, if used, purification, is filtered to remove polymer aggregates with a size greater than 125 micrometers.

[0067] use Also part of the present invention is the use of the aqueous polymer dispersions detailed hereinabove and / or obtainable from the process detailed hereinabove as opacifiers in liquid formulations and compositions. More specifically, such aqueous polymer dispersions are preferably used in the field of cleaning compositions for use on fabrics and / or hard surfaces, and for use in industrial and institutional cleaning.

[0068] A further part of the present invention is a liquid or semi-liquid formulation or composition comprising at least one aqueous polymer dispersion as detailed hereinbefore and / or an aqueous polymer dispersion obtainable from the process detailed hereinbefore for use in the field of cleaning compositions for use on fabrics and / or hard surfaces and for use in industrial and institutional cleaning. Preferably, such an aqueous polymer dispersion is used therein as an opacifier.

[0069] A further part of the present invention is a liquid or semi-liquid detergent composition comprising at least one aqueous polymer dispersion as detailed herein above and / or an aqueous polymer dispersion obtainable from the process detailed herein above, such composition being preferably a laundry detergent, hand dishwashing detergent, automatic dishwashing detergent or hard surface cleaner, more preferably for the home care and fabric care sector.

[0070] Preferably, such aqueous polymer dispersions are used as opacifiers therein.

[0071] Therefore, a preferred subject of the present invention is also the use of at least one aqueous polymer dispersion as detailed hereinbefore and / or an aqueous polymer dispersion obtainable from the process as detailed hereinbefore in fabric care and home care products, preferably in cleaning compositions and laundry treatments, laundry care products and laundry cleaning products, more preferably in laundry detergent formulations, even more preferably in liquid laundry detergent formulations. In particular, the aqueous polymer dispersions are used in such compositions / products / formulations to impart opacity.

[0072] Such inventive uses encompass the use of at least one aqueous polymer dispersion as detailed hereinabove and / or an aqueous polymer dispersion obtainable from the process detailed hereinabove, such polymer dispersion having a polymer structure similar to that described in all of its embodiments, variants, and preferred, more preferred etc. embodiments as detailed hereinabove.

[0073] Another subject of the present invention is therefore cleaning compositions, fabric care and home care products, preferably laundry cleaning compositions, laundry treatment products or laundry care products or laundry washing products, preferably liquid laundry detergent formulations or liquid laundry detergent products, comprising at least one aqueous polymer dispersion as detailed hereinbefore and / or an aqueous polymer dispersion obtainable from the process as detailed hereinbefore, which compositions or products exhibit improved opacity.

[0074] Such inventive compositions or products include at least one aqueous polymer dispersion as detailed hereinabove and / or an aqueous polymer dispersion obtainable from a process as detailed hereinabove, such polymer dispersions having similar polymer structures as described hereinabove in all of their embodiments, variants, and preferred, more preferred, etc. embodiments, as detailed hereinabove.

[0075] In one embodiment, cleaning compositions, fabric care and home care products, preferably laundry cleaning compositions, laundry treatment products or laundry care products or laundry cleaning products, more preferably liquid laundry detergent formulations or liquid laundry detergent products, comprising at least one aqueous polymer dispersion as detailed herein above and / or an aqueous polymer dispersion obtainable from a process as detailed herein above, wherein such compositions or products, preferably exhibiting improved opacity, additionally comprise at least one enzyme, preferably at least one protease, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, mannanases, xylanases, deoxyribonucleases, dispersins, pectinases, oxidoreductases, hemicellulases, phospholipases, esterases, cutinases, lactases and peroxidases, and combinations of at least two of the above types.

[0076] At least one aqueous polymer dispersion as detailed herein above, and / or obtainable from a process as detailed herein above, is present in said compositions and products of the present invention at a concentration of from about 0.01% to about 10%, preferably 0.02 to 5%, more preferably from about 0.05% to 3%, even more preferably from about 0.1% to about 2%, even more preferably from about 0.15% to about 2%, and most preferably in an amount of up to 1.5%, for example up to 1%, by weight based on the total weight of such composition or product, respectively, including all ranges generated by selecting any of the lower limits and any of the upper limits stated herein, and all values ​​therebetween; such compositions or products can further comprise, and preferably do comprise, a surfactant system, in an amount of from about 1% to about 70% by weight of the composition or product; and said compositions and products are for use as fabric care compositions.

[0077] Even more preferably, the composition or product of the present invention as detailed herein above, comprising at least one aqueous polymer dispersion as detailed herein above and / or an aqueous polymer dispersion obtainable from a process as detailed herein above, optionally further comprising at least one surfactant or surfactant system in an amount of from about 1% to about 70% by weight of the composition or product, for primary cleaning (i.e., soil removal) in laundry applications, which additionally comprises at least one enzyme preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, mannanases, xylanases, deoxyribonucleases, dispersins, pectinases, oxidoreductases, hemicellulases, phospholipases, esterases, pectinases, cutinases, lactases and peroxidases, and a combination of at least two of the aforementioned types, preferably at least one protease.

[0078] In one preferred embodiment, the cleaning composition of the present invention is a liquid or semi-liquid laundry detergent composition, preferably a liquid laundry detergent composition.

[0079] In one embodiment, the aqueous polymer dispersion of the present invention can be utilized in cleaning compositions or products comprising a surfactant system comprising C10-C15 alkylbenzene sulfonate (LAS) as the surfactant base and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants or mixtures thereof.

[0080] In a further embodiment, the aqueous polymer dispersion of the present invention can be utilized in cleaning compositions or fabric care and home care products, preferably laundry cleaning compositions, laundry care products or laundry treatment products or laundry cleaning products, preferably liquid laundry detergent formulations or liquid laundry detergent products, comprising C8 to C18 linear or branched alkyl ether sulfates having 1 to 5 ethoxy units as surfactant base and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants or mixtures thereof.

[0081] In one embodiment of the present invention, the aqueous polymer dispersion is a component of a cleaning composition or fabric care and home care product, preferably a laundry cleaning composition, laundry care product or laundry treatment product or laundry washing product, preferably a liquid laundry detergent formulation or liquid laundry detergent product, each further comprising at least one surfactant, preferably at least one anionic surfactant.

[0082] In a further embodiment, the present invention also encompasses a composition comprising the aqueous polymer dispersion described hereinabove, further comprising an antimicrobial agent as disclosed herein below, preferably selected from the group consisting of 2-phenoxyethanol, more preferably said antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition; even more preferably 0.1 to 2% phenoxyethanol.

[0083] In a further embodiment, the present invention also encompasses a method of preserving an aqueous composition against microbial contamination or growth, such composition comprising an aqueous polymer dispersion as described hereinabove, such composition being preferably a detergent composition, such method comprising adding at least one antimicrobial agent selected from the antimicrobial agents of the present disclosure as disclosed hereinafter, such antimicrobial agent preferably being 2-phenoxyethanol.

[0084] In a further embodiment, the present invention also encompasses a composition, preferably a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dishwashing composition, even more preferably a liquid laundry detergent composition or a liquid softener composition for use on laundry, such composition comprising an aqueous polymer dispersion as described hereinabove, such composition further comprising 4,4'-dichoro-2-hydroxydiphenyl ether at a concentration of 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6%, each by weight of the composition.

[0085] In a further embodiment, the present invention also encompasses a method of laundering fabrics or cleaning hard surfaces, the method comprising treating the fabrics or hard surfaces with a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dishwashing composition, even more preferably a liquid laundry detergent composition or a liquid softener composition for use on laundry, such composition comprising the aqueous polymer dispersion described hereinabove, such composition further comprising 4,4'-dichoro 2-hydroxydiphenyl ether.

[0086] The selection of additional surfactants and further cleaning adjuncts in these embodiments can depend on the application and the desired benefit.

[0087] Preferably, the cleaning compositions of the present invention are in the field of laundry cleaning compositions and detergents for laundry and hand dish cleaning compositions. More preferably, the cleaning compositions of the present invention are liquid compositions for use in the field of laundry and hard surface cleaning, such as liquid laundry detergents and liquid dishwashing cleaning compositions, preferably for hand dish washing and laundry.

[0088] The cleaning composition may have a form selected from liquid, powder, single or multi-phase unit dose, sachet, tablet, gel, paste, bar or flake. Preferred cleaning compositions are liquid or semi-liquid. More preferred cleaning compositions are liquid.

[0089] Industrial and institutional cleaning compositions and formulations include those designed to clean any type of soiled material or surface, for example, hard surface cleaners for any type of surface such as tiles, carpets, PVC surfaces, wooden surfaces, metal surfaces, lacquered surfaces, etc.

[0090] The cleaning composition comprises a surfactant system in an amount sufficient to impart the desired cleaning properties, hi some embodiments, the cleaning composition comprises from about 1% to about 70% of the surfactant system by weight of the composition.

[0091] In other embodiments, the liquid cleaning composition comprises from about 2% to about 60% surfactant system by weight of the composition. In further embodiments, the cleaning composition comprises from about 5% to about 30% surfactant system by weight of the composition. The surfactant system may comprise a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, and combinations thereof. Those skilled in the art will appreciate that a detersive surfactant includes any surfactant or mixture of surfactants that aids in cleaning, stain removal, or laundering soiled materials.

[0092] The cleaning composition may also contain auxiliary cleaning additives. Suitable auxiliary cleaning additives include builders, structurants or thickeners, mud soil removal / anti-redeposition agents, polymeric soil release agents, polymeric dispersants, polymeric grease cleaning agents, enzymes, enzyme stabilizing systems, bleaching compounds, bleaches, bleach activators, bleach catalysts, brighteners, dyes, hueing agents, color transfer inhibitors, chelating agents, suds suppressors, fabric softeners, and fragrances.

[0093] Such cleaning compositions, their components, their general compositions and more specific compositions are all known and are shown, for example, in publications 800542 and 800500 published by Protegas, Liechtenstein, and WO 2022 / 136409 and WO 2022 / 136408. If an opacifying compound is actually used therein or is simply intended to be used therein, it can be partially or completely replaced by the aqueous polymer dispersion of the present invention, and if not used, the aqueous polymer dispersion of the present invention can be added in the amount indicated in the present invention. These aforementioned documents also disclose various types of formulations for cleaning compositions, and all types of such compositions can be equally applied to the cleaning compositions intended herein.

[0094] In each of the aforementioned fields of application and compositions and formulations thereof, the aqueous polymer dispersions of the present invention are preferably used as opacifiers to impart opacity to such compositions and formulations, for example to impart turbidity to otherwise clear liquid formulations or formulations containing undissolved or emulsified components, thus "hiding" the undissolved or emulsified portions of the composition or formulation by imparting turbidity and making such portions less noticeable, or, if transparent (preferably colorless or only lightly colored), to enhance the visibility of the formulation or composition by imparting turbidity. Turbidity can also be utilized to change the visual observation of color by imparting turbidity, thus creating a different perception of such color by increasing the amount of scattered light, for example by enhancing color, reducing gloss, etc.

[0095] As used herein, the phrase "cleaning composition" includes compositions and formulations designed for cleaning soiled materials, including those designed to clean any type of soiled material or surface, and specifically including fabric care and home care compositions.

[0096] Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric cleaning compositions, laundry pre-wash detergents, laundry pre-treatments, laundry aids, spray products, dry cleaning agents or compositions, laundry rinse additives, washing additives, post-rinse fabric treatments, ironing aids, dishwashing compositions, hard surface cleaning compositions, unit dose formulations, delayed delivery formulations, detergents contained on or within porous substrates or nonwoven sheets, and other suitable forms that will be apparent to those skilled in the art in view of the teachings herein. Such compositions can be used in pre-wash treatments, post-wash treatments, or can be added during the rinse or wash cycle of a laundry operation.

[0097] "Industrial and institutional cleaning" compositions include those cleaning compositions designed for use in industrial and institutional cleaning, for example, for use in cleaning any type of soiled material or surface, such as hard surface cleaners for any type of surface, including tile, carpet, PVC surfaces, wood surfaces, metal surfaces, lacquered surfaces, etc.

[0098] The phrase "fabric care composition" is meant to include compositions and formulations designed to treat fabrics. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancement compositions, fabric cleaning compositions, laundry pre-wash agents, laundry pre-treatment agents, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, washing additives, post-rinse fabric treatment agents, ironing aids, unit dose formulations, delayed delivery formulations, detergents contained on or in porous substrates or nonwoven sheets, and other suitable forms that may be apparent to those skilled in the art in light of the teachings herein and the detailed description herein below. Such compositions may be used as laundry pre-treatment agents, laundry post-treatment agents, or may be added during the rinse or wash cycle of laundry operations, as further detailed herein below when describing the uses and applications of the aqueous polymer dispersions of the present invention and compositions comprising such dispersions.

[0099] "Fabric care and home care compositions" include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric refreshing compositions, laundry pre-wash detergents, laundry pre-treatments, laundry aids, spray products, dry cleaning agents or compositions, laundry rinse additives, washing additives, post-rinse fabric treatments, ironing aids, dishwashing compositions, hard surface cleaning compositions, unit dose formulations, delayed delivery formulations, detergents contained on or in porous substrates or nonwoven sheets, light-duty liquid detergent compositions, heavy-duty liquid detergent compositions, detergent gels commonly used in laundry applications, bleaching compositions, laundry aids, fabric enhancer compositions, and other suitable forms that would be apparent to one skilled in the art in light of the teachings herein. Such compositions can be used as laundry pre-treatments, post-laundry treatments, or can be added during the rinse or wash cycle of a laundry operation, preferably during the wash cycle of a laundry or dishwashing operation. More preferably, such compositions for fabric care and home care are laundry cleaning compositions, laundry care products or laundry washing products, most preferably liquid laundry detergent formulations or liquid laundry detergent products.

[0100] The cleaning compositions of the present invention can be in any form, i.e., "liquid" compositions, including types of liquid-containing compositions such as pastes, gels, emulsions, foams, and mousses; solid compositions such as powders, granules, microcapsules, beads, noodles, pearlized balls, agglomerates, tablets, granular compositions, sheets, pastilles, beads, fibrous articles, bars, flakes, or mixtures thereof; types delivered in single-compartment, dual-compartment, or multi-compartment sachets or containers; single-phase or multi-phase unit dose articles; spray or foam detergents; wet wipes (i.e., a cleaning composition combined with a nonwoven material such as those described in U.S. Pat. No. 6,121,165 to Mackey et al.); dry wipes (i.e., a cleaning composition combined with a nonwoven material such as those described in U.S. Pat. No. 5,980,931 to Fowler et al.) that are activated by wetting with water by the user or consumer; or other homogeneous, heterogeneous, or single-phase or multi-phase cleaning products.

[0101] The compositions can be enclosed in single or multi-compartment pouches. Multi-compartment pouches can have at least two, at least three, or at least four compartments. Multi-compartment pouches include side-by-side and / or nested compartments. The compositions contained in the pouches or their compartments can be liquid, solid (such as powder), or a combination thereof.

[0102] Non-limiting examples of "liquids" / "liquid compositions" include light and heavy duty liquid detergent compositions, fabric enhancers, detergent gels commonly used for laundry, bleaches, and laundry aids. Gases, e.g., suspended bubbles, or solids, e.g., particles, can be contained within the liquid.

[0103] The liquid cleaning compositions of the present invention preferably have a viscosity of 50 to 10,000 mPa·s, with liquid hand dish cleaning compositions (also liquid manual "dishwashing compositions") preferably having a viscosity of 100 to 10,000 mPa·s, more preferably 200 to 5,000 mPa·s, and most preferably 500 to 3,000 mPa·s at 20 l / s and 20°C; and liquid laundry cleaning compositions preferably having a viscosity of 50 to 3,000 mPa·s, more preferably 100 to 1,500 mPa·s, and most preferably 200 to 1,000 mPa·s at 20 l / s and 20°C.

[0104] The liquid cleaning compositions of the present invention can have any suitable pH value. Preferably, the pH of the composition is adjusted to 4 to 14. More preferably, the composition has a pH of 6 to 13, even more preferably 6 to 10, and most preferably 7 to 9. The pH of the composition can be adjusted using pH-adjusting ingredients known in the art, measured as a 10% product concentration in demineralized water at 25°C. For example, NaOH can be used, and the actual weight percent of NaOH can be varied to achieve a desired pH, such as pH 8.0. In one embodiment of the present invention, the pH can be adjusted to above 7 by using amines, preferably alkanolamines, more preferably triethanolamine.

[0105] Cleaning compositions, such as fabric care and home care products and formulations for industrial and institutional cleaning, more specifically laundry and hand dish detergents, are known to those skilled in the art. Any compositions related to the respective applications known to those skilled in the art can be used in the context of the present invention by including at least one polymer of the present invention, preferably at least one polymer, in an amount suitable for imparting certain properties to such compositions, especially when such compositions are used in their field of application.

[0106] An aspect of the present invention is also the use of the polymers of the present invention as additives or single dose agents for laundry detergent formulations, in particular for liquid detergent formulations, preferably concentrated liquid detergent formulations.

[0107] The cleaning compositions of the present invention may, and preferably do, contain auxiliary cleaning additives (sometimes abbreviated herein as "adjuvants"), such adjuvants preferably being in addition to the surfactant system defined above.

[0108] Suitable auxiliary cleaning additives include builders, co-builders, surfactant systems, fatty acids and / or their salts, structuring agents, thickeners and rheology modifiers, viscosity / stain removal / anti-redeposition agents, polymeric soil release agents, dispersing agents such as polymeric dispersants, polymeric greasy soil cleaning agents, solubilizing agents, amphiphilic copolymers (including those without vinylpyrrolidone), chelating agents, enzymes, enzyme stabilizing systems, encapsulated benefit agents such as encapsulated fragrances, bleaching compounds, bleaches, bleach activators, bleach catalysts, catalytic materials, brighteners, malodor control agents, pigments, dyes, opacifiers, pearlizing agents, hueing agents, dye transfer inhibitors, fabric softeners, carriers, suds boosters, suds suppressors (defoamers), color speckle, silver care (silver care), care), rust and / or corrosion inhibitors, alkalinity sources, pH adjusters, pH buffers, hydrotropes, scrubbing particles, antibacterial and antimicrobial agents, preservatives, antioxidants, softening agents, carriers, fillers, solvents, processing aids, pro-fragrance, and fragrances.

[0109] Suitable examples of such cleaning adjuvants and amounts to be used are described, for example, in WO 99 / 05242, US Pat. Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1.

[0110] Such cleaning compositions, their components, including (auxiliary) cleaning additives, their general and more specific compositions are all known in principle and are shown, for example, in publications 800542 and 800500 published by Protegas, Liechtenstein, and in WO 2022 / 136409 and WO 2022 / 136408. In any of these prior art documents, the opacifiers in the general compositions and in the individual specific cleaning compositions disclosed in the aforementioned publications can be partially or completely replaced by the dispersions of the present invention. In these prior art documents, various types of formulations for cleaning compositions are also disclosed, and all such types of compositions, both the general compositions and also the individual specific cleaning compositions, can be equally applied to the cleaning compositions discussed herein.

[0111] The present invention therefore also encompasses any and all disclosed compositions of the aforementioned prior art disclosures, but further comprising at least one dispersion of the present invention in addition to or as an alternative to the opacifiers contained in such prior art compositions, which can be replaced by such dispersions of the present invention, such replacement being known in principle to those skilled in the art. The content of the dispersion of the present invention is generally present in the formulation at a concentration of 0.05 to 20% by weight, preferably at most 10% by weight, more preferably 0.1 to 5% by weight, even more preferably 0.5 to 2% by weight, and most preferably at most 1% by weight.

[0112] In addition to the surfactant system and graft polymer, the liquid cleaning composition may additionally comprise, and preferably comprises at least one of, rheology control / regulators, emollients, moisturizers, skin rejuvenation actives, and solvents.

[0113] The solid composition may additionally comprise, and preferably comprises at least one of, a filler, a bleaching agent, a bleach activator, and a catalytic material.

[0114] Those skilled in the art will appreciate that a detersive surfactant includes any surfactant or mixture of surfactants that aids in cleaning, stain removal or laundering soiled materials.

[0115] Thus, cleaning compositions of the present invention, such as fabric care and home care products and industrial and institutional cleaning formulations, more particularly laundry and hand dish detergents, preferably additionally comprise a surfactant system, and more preferably also further adjuvants.

[0116] The surfactant system may be comprised of one surfactant or a combination of surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and combinations thereof. Those skilled in the art will understand that a detergent surfactant system encompasses any surfactant or mixture of surfactants that provides cleaning, stain removal, or laundering benefits to soiled materials.

[0117] The cleaning compositions of the present invention preferably contain a surfactant system in an amount sufficient to provide the desired cleaning properties. In some embodiments, the cleaning composition comprises from about 1% to about 70% of the surfactant system by weight of the composition. In other embodiments, the liquid cleaning composition comprises from about 2% to about 60% of the surfactant system by weight of the composition. In further embodiments, the cleaning composition comprises from about 5% to about 30% of the surfactant system by weight of the composition. The surfactant system may comprise a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and combinations thereof.

[0118] The cleaning compositions of the present invention may comprise, in addition to all other ingredients mentioned, one or more enzymes, more preferably a protease and / or amylase, selected from those disclosed hereinabove, and even more preferably the protease is a protease having at least 90% sequence identity to SEQ ID NO: 22 of EP1921147B1 and having the amino acid substitution R101E (according to BPN' numbering) and the amylase is an amylase having at least 90% sequence identity to SEQ ID NO: 54 of WO2021032881A1, and such enzymes are preferably present in the formulation at a level of from about 0.00001% to about 5% by weight of enzyme protein, preferably from about 0.00001% to about 2% by weight, more preferably from about 0.0001% to about 1% by weight, or even more preferably from about 0.001% to about 0.5% by weight, based on the weight of the composition.

[0119] The following compositions shown below, including those in the tables, disclose certain types of general cleaning compositions, corresponding to typical compositions associated with typical cleaning conditions as typically used in various regions and countries of the world. At least one dispersion of the present invention can be added to such formulations in a suitable amount as outlined herein. If the composition shown does not contain a dispersion of the present invention, such a composition is a comparative example composition. If it contains a dispersion of the present invention in an amount described herein as a particularly preferred, more preferred, etc. range, such a composition is considered to fall within the scope of the present invention.

[0120] (In all weight percentages below; if the ingredients are added as solutions or dispersions, the percentages relate to the active substance content, i.e., usually the solids content of the ingredients in such solutions or dispersions)

[0121] The liquid laundry detergent according to the present invention comprises: 0.05 to 5% of at least one aqueous polymer dispersion (% by solids); 0.05 to 10% of at least one cleaning polymer; 1 to 50% surfactant, 0.1 to 40% of a builder, cobuilder and / or chelating agent; With 0.1 to 50% of other adjuvants, Water until 100% It consists of:

[0122] Preferred liquid laundry detergents according to the present invention include: 0.15 to 3% of at least one aqueous polymer dispersion (% by solids); 0.2 to 10% of at least one cleaning polymer; an anionic surfactant selected from 5 to 40% of C10 to C15-LAS and C10 to C18 alkyl ether sulfates containing 1 to 5 ethoxy units; 1.5 to 10% of a nonionic surfactant selected from C10 to C18 alkyl ethoxylates containing 3 to 10 ethoxy units; 2-20% of a soluble organic builder / cobuilder selected from C10-C18 fatty acids, di- and tricarboxylic acids, hydroxydi- and hydroxytricarboxylic acids, aminopolycarboxylates, and polycarboxylic acids; an enzyme system comprising 0.05 to 5% of at least one enzyme suitable for detergent applications, preferably further comprising an enzyme stabilizing system; 0.5 to 20% of a mono- or diol selected from ethanol, isopropanol, ethylene glycol or propylene glycol; With 0.1 to 20% of other adjuvants, Water until 100% It consists of:

[0123] In a preferred embodiment, at least one compound according to the invention is used in a hand dish detergent.

[0124] The liquid hand dish detergent according to the present invention comprises: 0.05 to 5% of at least one dispersion of the present invention; 1 to 50% surfactant, With 0.1 to 50% of other adjuvants, Water until 100% It consists of:

[0125] Preferred liquid hand dish detergents according to the present invention include: 0.2 to 1% of at least one dispersion of the present invention; 5 to 40% of an anionic surfactant selected from C10 to C15-LAS, C10 to C18 alkyl ether sulfates containing 1 to 5 ethoxy units, and C10 to C18 alkyl sulfates; 2-10% cocamidopropyl betaine, 0-10% lauramine oxide, 0-2% of a nonionic surfactant, preferably a C10-Guerbet alcohol alkoxylate; 0-5% of an enzyme, preferably an amylase, and preferably also an enzyme stabilizing system; 0.5 to 20% of a mono- or diol selected from ethanol, isopropanol, ethylene glycol or propylene glycol; With 0.1 to 20% of other adjuvants, Water until 100% It consists of:

[0126] [Table 1]

[0127] [Table 2]

[0128] Further exemplary liquid detergent formulations LD1, LD2 and LD3 are shown in the following three tables:

[0129] [Table 3]

[0130] [Table 4]

[0131] [Table 5]

[0132] In all three tables above: * (60% by weight of vinyl acetate grafted onto polyethylene glycol with an Mn of 6000 g / mol as the graft substrate (based on the total weight of the polymer); produced according to the general disclosure of WO 2007138054 A1)

[0133] [Table 6]

[0134] Preferably, in each laundry detergent, cleaning composition and / or fabric and home care product, the at least one aqueous polymer dispersion is present at a concentration, by weight based on the total weight of such composition or product, respectively, of from about 0.01% to about 10%, preferably from about 0.02% to 5%, more preferably from about 0.05% to about 3%, even more preferably from about 0.1% to about 2%, even more preferably from about 0.15% to about 2%, and most preferably up to 1.5%, e.g., up to 1%, including all ranges resulting from selecting either the lower and upper limits and all values ​​therebetween recited.

[0135] Specific embodiments as described throughout this disclosure are encompassed by the present invention as part of the present invention; various additional options disclosed herein as "optional," "preferred," "more preferred," "even more preferred," or "most preferred" options of specific embodiments may be selected individually and independently (unless such independent selection is impossible by the nature of the feature or where such independent selection is expressly excluded) and therefore may be combined within any of the other embodiments (where other such options and preferences may also be selected individually and independently), and each and any and all such possible combinations are included as individual embodiments as part of the present invention.

[0136] Most Preferred Embodiment Claim 1 below, a) an ethylenically unsaturated monomer M, (1) (M1) at least one vinyl ester, preferably comprising vinyl acetate, more preferably comprising at least 50%, even more preferably at least 90% vinyl acetate; and (2) (M2) at least one (meth)acrylic acid ester, optionally containing methacrylic acid as a minor component, in which the (meth)acrylic acid in the methacrylic acid ester is linked via an ether functional group to a polyalkylene oxide derived block (PAO), the PAO consisting of 2 to 40 alkylene oxide (AO), most preferably 25 AO-units, the PAO preferably being linked via the ether functional group to a C1 to C24, preferably at least C4, more preferably at least C6, even more preferably C8 to C24-aliphatic alkanol, Most preferably further bonded to a C18-aliphatic alkanol, AO preferably selected from EO, PO and / or BuO, more preferably at least EO in an amount of from 50% by weight, more preferably at least 75% by weight, even more preferably at least 90% by weight, most preferably essentially EO, based on the total AO; preferably containing methacrylic acid, more preferably methacrylic acid ester and free methacrylic acid in a ratio of about 70% by weight / 30% to 80% by weight / 20% by weight, more preferably about 75% by weight / 25% by weight; (3) (M3) Optional further monomer (preferably absent) polymerizable with M1 and M2 an ethylenically unsaturated monomer M comprising: b) 1 to 15% by weight, preferably 2 to 10% by weight, more preferably 3 to 8% by weight, and most preferably 4 to 6% by weight, based on the total weight of (CGCC) monomer M, of carboxyl group-containing compounds selected from compounds having at least 3, more preferably at least 6, 8, 10, 15, 20, 25... carboxyl groups in their structure, in which at least 10 percent and at most 90 percent of the carboxyl groups are deprotonated (and thus form salts with counterions selected from Na, K, NH4, Mg, Ca...), and which are selected from compounds such as citric acid, isocitric acid; ethylenediaminetetraacetic acid; nitriloacetic acid; tartaric acid; oligomeric and polyacrylic acids; oligomeric and polymethacrylic acids; trimellitic acid; oligomeric amino acids containing carboxy groups, such as polyaspartic acid; oligomeric and polyglutamic acid; carboxylated oligomeric and polymeric sugars such as oxidized starch (a mixture of amylopectin and amylose); polyglucuronates; cellulose oxidized to celluronate; natural polycarboxylic polysaccharides such as xylan; pectinic acid; alginic acid; carboxymethylated polysaccharides based on 1,4-polyglucan, 1,3-polyglucan, and 1,6-polyglucan; polyuronic acids based on 1,4-polyglucan, 1,3-polyglucan, and 1,6-polyglucan; polygalacturons; carboxyl-containing compounds, preferably selected from the group including carboxylated polysaccharides, more preferably carboxylated cellulose, and even more preferably carboxylated methylcellulose (carboxymethylcellulose, "CMC"); and c) (S) at least one (non-carboxylated) sugar and / or polysaccharide, such as glucose, starch degradation products, maltodextrin, in an amount of 2 to 50% by weight, preferably 5 to 35% by weight, more preferably 10 to 30% by weight, most preferably 15 to 25% by weight, based on the total weight of the monomer M, and d) at least one emulsifier selected from nonionic and anionic surfactants, i) at least one nonionic surfactant, anionic emulsifiers having at least one anionic group selected from phosphate, phosphonate, sulfate and sulfonate groups; anionic emulsifiers, typically used in the form of their alkali metal salts, in particular their sodium salts, or in the form of their ammonium salts; Preferably, anionic emulsifiers have at least one sulfate or sulfonate group or at least one phosphate or phosphonate group, more preferably at least one sulfonate or sulfate group, and most preferably only one sulfonate or sulfate group. is selected from a) anionic emulsifiers having at least one sulfate or sulfonate group are preferably - salts of alkyl sulfates, in particular C8 to C22 alkyl sulfates, in particular alkali metal and ammonium salts, - the salts, in particular the alkali metal and ammonium salts, of sulfuric acid monoesters of C2-C3 alkoxylated alkanols, in particular of sulfuric acid monoesters of C2-C3 alkoxylated C8-C22 alkanols, preferably having a C2-C3 alkoxylation level (AO level) ranging from 2 to 40, - sulfuric acid monoesters of C2-C3 alkoxylated alkylphenols, in particular the salts of sulfuric acid monoesters of C2-C3 alkoxylated C4-C18-alkylphenols, in particular the alkali metal and ammonium salts (AO level preferably 3-40), - salts, in particular alkali metal and ammonium salts, of alkylsulfonic acids, in particular C8-C22-alkylsulfonic acids; - salts, especially alkali metal and ammonium salts, of dialkyl esters, in particular di-C4-C18-alkyl esters of sulfosuccinic acid, - salts, in particular alkali metal and ammonium salts, of alkylbenzenesulfonic acids, in particular C4 to C22 alkylbenzenesulfonic acids, and - salts, especially alkali metal and ammonium salts, of mono- or disulfonated alkyl-substituted diphenyl ethers, for example bis(phenylsulfonic acid) ethers having a C4-C24 alkyl group on one or both aromatic rings; (The term "C2-C3 alkoxylated" means that the compound is ethoxylated, propoxylated or coethoxylated / propoxylated, i.e., that the compound is obtained by a process that introduces polyethylene oxide, polypropylene oxide or poly(ethylene oxide-co-propylene oxide) groups, respectively.) Selected from; b) anionic emulsifiers having at least one phosphate or phosphonate group are preferably salts, especially alkali metal and ammonium salts, of mono- and dialkyl phosphates, in particular C8-C22-alkyl phosphates, - phosphoric acid monoesters of C2-C3-alkoxylated alkanols, preferably having an alkoxylation level in the range from 2 to 40, in particular from 3 to 30, such as phosphoric acid monoesters of ethoxylated C8-C22 alkanols, preferably having an ethoxylation level (EO level) in the range from 2 to 40, phosphoric acid monoesters of propoxylated C8-C22 alkanols, preferably having a propoxylation level (PO level) in the range from 2 to 40, and salts, in particular alkali metal and ammonium salts, of phosphoric acid monoesters of ethoxylated-co-propoxylated C8-C22 alkanols, preferably having an ethoxylation level (EO level) in the range from 1 to 20 and a propoxylation level of 1 to 20, salts of phosphoric acid monoesters of C2-C3-alkoxylated alkylphenols, in particular salts of phosphoric acid monoesters of C2-C3-alkoxylated C4-C18-alkylphenols, in particular alkali metal and ammonium salts (AO level preferably 3-40); salts, in particular alkali metal and ammonium salts, of alkylphosphonic acids, in particular C8-C22-alkylphosphonic acids, and - salts of alkylbenzenephosphonic acids, in particular C4-C22-alkylbenzenephosphonic acids, in particular alkali metal and ammonium salts Selected from; More preferred anionic emulsifiers are those from the following group: - salts of alkyl sulfates, in particular C8 to C22 alkyl sulfates, in particular alkali metal and ammonium salts, the salts, especially alkali metal salts, of sulfuric acid monoesters of C2-C3-alkoxylated alkanols, in particular of sulfuric acid monoesters of C2-C3-alkoxylated C8-C22-alkanols, preferably having an AO level in the range from 2 to 40; - sulfuric acid monoesters of C2-C3-alkoxylated alkylphenols, in particular those of C2-C3-alkoxylated C4-C18-alkylphenols (AO level preferably 3-40); alkylbenzenesulfonic acids, in particular C4-C22 alkylbenzenesulfonic acids, and - For example, mono- or disulfonated alkyl-substituted diphenyl ethers of bis(phenylsulfonic acid) ethers having a C4-C24 alkyl group on one or both aromatic rings. Selected from; ii) at least one nonionic surfactant for example, - C2-C3-alkoxylated mono-, di- and trialkylphenols, the number of repeating units of which in the alkylene oxide derived moiety is preferably 3 to 50 and / or the alkyl groups are preferably C4-C10-alkyl; - C2-C3 alkyloxates of long-chain alcohols, such as ethoxylates, propoxylates or ethoxylate-co-propoxylates, in which the number of repeating units of the alkylene oxide-derived moiety is preferably 3 to 100 and / or the alkyl group is preferably C8 to C36-alkyl, and polyethylene oxide / polypropylene oxide homo- and copolymers, which may contain alkylene oxide units copolymerized in random distribution or in the form of blocks or mixtures of homoblocks and random blocks; More preferred are those in which the alkyl group C8 to C30 has an average alkoxylation level of 5 to 100, and particularly preferred among these are those having a linear C12 to C20 alkyl group and an average alkoxylation level of 10 to 50, C2 to C3-alkoxylated monoalkylphenols, and C2 to C3-alkoxylated long-chain alkanols. an emulsifier selected from aromatic aliphatic or aliphatic nonionic emulsifiers selected from: and e) optionally sulfate ions, and f) optionally sulfite ions and preferably the amount of M1 is between 80 and 99.99 mol %, more preferably the amount of M1 is at least 98% and the amount of M2 is 0.001 to 20 mol% , more preferably 0.1, even more preferably 0.2, even more preferably 0.5, most preferably 0.7, preferably at most 10, even more preferably at most 5, more preferably at most 2%, most preferably the amount of M1 is about 99% by weight, the amount of M2 is about 1% by weight, and the total amount of M1+M2 is 100% by weight; and The aqueous polymer dispersion, wherein the dispersion has, after completion of polymerization, a pH of at most 4, more preferably less than 4, even more preferably at most 3.8, even more preferably at most 3.6, more preferably at least 2.5, even more preferably at least 3, even more preferably at least 3.2, and most preferably at least 3.4.

[0137] Embodiment 2: (M1) the vinyl ester monomer comprises at least 50%, and even more preferably at least 90%, vinyl acetate, based on the total molar amount of vinyl esters; and (M2) at least one (meth)acrylic acid ester is (meth)acrylic acid linked via an ether functional group to a polyalkylene oxide derived block (PAO), the PAO consisting of 20 to 30 alkylene oxides (AO), most preferably 25 AO units, the PAO being preferably further linked via an ether functional group to a C14 to C22 aliphatic alkanol, most preferably a C16 / 18 aliphatic alkanol, the AO being selected from EO and PO and / or BuO, more preferably EO and PO, the EO being in an amount of from 75% by weight, more preferably at least 90% by weight, most preferably essentially EO, based on the total AO; and further comprising methacrylic acid, the methacrylic acid ester and free methacrylic acid being in a ratio of about 70% by weight / 30% to 80% by weight / 20% by weight, more preferably about 75% by weight / 25% by weight, and The dispersion of claim 1, wherein (M3) is not included.

[0138] Embodiment 3: (M1) the vinyl ester monomer comprises at least 90% vinyl acetate, preferably essentially only vinyl acetate, based on the total molar amount of vinyl esters; and (M2) The dispersion of embodiment 2, wherein the at least one (meth)acrylic acid ester is (meth)acrylic acid linked via an ether functionality to a polyalkylene oxide derived block (PAO), the PAO consisting of 23 to 27 alkylene oxides (AO), most preferably an average of 25 AO units, and the PAO is preferably further linked via an ether functionality to a C16 / 18-aliphatic alkanol, most preferably a C16 / 18-aliphatic alkanol, the AO consisting essentially of EO; and further comprising methacrylic acid, wherein the methacrylic acid ester and free methacrylic acid are in a ratio of about 70% / 30% to 80% / 20% by weight, more preferably about 75% / 25% by weight.

[0139] Embodiment 4: (M1) is vinyl acetate, and (M2) The dispersion according to embodiment 3, wherein the at least one (meth)acrylic acid ester is methacrylic acid bonded to a polyethylene oxide block (PEO) via an ether functional group, the PEO consisting of an average of 25 AO units, the PEO further bonded to a C16 / 18-aliphatic alkanol via an ether functional group, and further comprising methacrylic acid, wherein the methacrylic acid ester and free methacrylic acid are in a ratio of about 75% / 25% by weight.

[0140] Embodiment 5: 5. The dispersion of any one of embodiments 1 to 4, wherein (CGCC) is a carboxyl group-containing compound selected from carboxylated polysaccharides, more preferably carboxylated celluloses, and even more preferably carboxylated methylcellulose (carboxymethylcellulose, "CMC"), in an amount of preferably 2.5 to 10 wt. %, most preferably about 5 wt. %, based on the total amount of monomers (M1+M2+M3).

[0141] Embodiment 6: 6. The dispersion of any of embodiments 1-5, wherein the dispersed polymer particles have a D[4,3] value determined by static light scattering of at least 400 and up to 1000 nm.

[0142] Embodiment 7: 7. The dispersion according to any one of embodiments 1 to 6, wherein the (S) at least one saccharide and / or polysaccharide is a starch degradation product, preferably maltodextrin, in an amount of 10 to 30% by weight, preferably 15 to 25% by weight, more preferably 17 to 23% by weight, based on the total weight of the monomers M.

[0143] Embodiment 8: 8. The dispersion of embodiment 7, wherein (S) is a degraded starch having a dextrose equivalent according to Lane and Eynon in the range of 2 to 40%.

[0144] Embodiment 9: 10. The dispersion according to embodiment 9, wherein (S) is a maltodextrin having a DE value of 10 to 30, preferably 12 to 16 or 25 to 30.

[0145] Embodiment 10: 9. The dispersion according to any one of the preceding embodiments, wherein as compound S a degraded starch is utilized having a number average molecular weight in the range of 300 to 2000 Daltons, determined by osmometry, preferably in the range of 5 to 150, more preferably at most 70, even more preferably at most 50, more preferably from 10, even more preferably from 15, and most preferably from 20, in weight percent based on the total weight of monomers M1+M2+M3, respectively.

[0146] Embodiment 11: The following characteristics: a) to d): a) a transmittance of 525 nm wavelength light of at least 20% when measured as a 0.01% by weight dispersion in water; b) a pH of 2.5 to 9, preferably from 3, more preferably from 3.3, and more preferably up to 7, even more preferably up to 6, even more preferably up to 5, most preferably about 3.5; c) a density of 1.04 to 1.08 g / mL measured as a 10 wt% dispersion (solids basis), and d) Viscosity of 30 to 1000 mPas (Brookfield viscosity, spindle 3; measured as a 10% by weight dispersion; based on solids; concentration of 30% by weight active substance) 11. The dispersion of any one of embodiments 1 to 10, having at least one of:

[0147] Embodiment 12: 12. A process for producing a polymer dispersion according to any one of embodiments 1 to 11, comprising: A) an ethylenically unsaturated monomer M, (1) (M1) at least one vinyl ester, preferably comprising vinyl acetate, more preferably comprising at least 50%, even more preferably at least 90% vinyl acetate; and (2) (M2) at least one (meth)acrylic acid ester, optionally containing methacrylic acid as a minor component, in which the (meth)acrylic acid in the methacrylic acid ester is linked via an ether functional group to a polyalkylene oxide derived block (PAO), the PAO consisting of 2 to 40 alkylene oxide (AO), most preferably 25 AO-units, the PAO preferably being linked via the ether functional group to a C1 to C24, preferably at least C4, more preferably at least C6, even more preferably C8 to C24-aliphatic alkanol, Most preferably further bonded to a C18-aliphatic alkanol, AO preferably selected from EO, PO and / or BuO, more preferably at least EO in an amount of from 50% by weight, more preferably at least 75% by weight, even more preferably at least 90% by weight, most preferably essentially EO, based on the total AO; preferably containing methacrylic acid, more preferably methacrylic acid ester and free methacrylic acid in a ratio of about 70% by weight / 30% to 80% by weight / 20% by weight, more preferably about 75% by weight / 25% by weight; (3) (M3) Optional further monomer (preferably absent) polymerizable with M1 and M2 an ethylenically unsaturated monomer M comprising: at least one emulsifier, - water, - 1 to 15% by weight, preferably 2 to 10% by weight, more preferably 3 to 8% by weight, and most preferably 4 to 6% by weight, based on the total weight of the (CGCC) monomer M, of carboxyl group-containing compounds selected from compounds having at least 3, more preferably at least 6, 8, 10, 15, 20, 25... carboxyl groups in their structure, in which at least 10 percent and at most 90 percent of the carboxyl groups are deprotonated (and thus form salts with counterions selected from Na, K, NH4, Mg, Ca...), and which are selected from citric acid, isocitric acid; ethylenediaminetetraacetic acid; nitriloacetic acid; tartaric acid; oligomeric and polyacrylic acids; oligomeric and polymethacrylic acids; trimellitic acid; oligomeric amino acids containing carboxy groups, such as polyaspartic acid; oligomeric and polyglutamine acids; oligomers and polyacetates having carboxy groups, such as poly(glyoxylic)aldehyde; carboxylated oligomeric and polymeric sugars, such as oxidized starch (a mixture of amylopectin and amylose); polyglucronates; cellulose oxidized to celluronate; natural polycarboxylic polysaccharides, such as xylan; pectinic acid; alginic acid; carboxymethylated polysaccharides based on 1,4-, 1,3-, and 1,6-polyglucans; polyuronic acids based on 1,4-, 1,3-, and 1,6-polyglucans; polygalacturons; carboxyl-containing compounds, preferably selected from the group including carboxylated polysaccharides, more preferably carboxylated cellulose, and even more preferably carboxylated methylcellulose (carboxymethylcellulose, "CMC"); and (S) at least one (non-carboxylated) sugar and / or polysaccharide, such as glucose, starch degradation products, maltodextrin, in an amount of 2 to 50% by weight, preferably 5 to 35% by weight, more preferably 10 to 30% by weight, most preferably 15 to 25% by weight, based on the total weight of the monomers M; In the presence of polymerizing using at least one radical initiator, or preferably a radical initiator pair comprising a peroxide and a reducing compound; Such polymerization is - in a reaction vessel equipped with either a pressurizing device and / or a device for controlling the boiling of the components, by which means the components can be contained in the reaction vessel during reaction at high temperature; - at a temperature of 60-90, preferably 70-80 ° C; at a pH of at most 4, more preferably below 4, even more preferably at most 3.8, even more preferably at most 3.6 the steps to be performed; Furthermore B) optionally adding additional radical initiator or initiator couple to further reduce the content of unreacted monomer and / or reduce the color of the resulting polymer dispersion; C) optionally adding at least one further reducing compound to reduce the color of the resulting polymer dispersion; D) optionally adding at least one further additive that may be required or desired as an additional component into the resulting polymer dispersion; E) optionally carrying out a step of removing volatilizable compounds from the reaction mixture by using a distillation step and / or a stripping step using steam or gas, preferably steam; F) optionally filtering the polymer dispersion from the previous step, preferably using a 125 micrometer filter; wherein an aqueous polymer dispersion is obtained.

[0148] Embodiment 13: 13. The process of embodiment 12, wherein for the main polymerization step, at least one persulfate and ascorbic acid and / or isoascorbic acid are used as radical polymerization initiators.

[0149] Embodiment 14: 14. The process of embodiment 12 or 13, wherein the radical polymerization initiator additionally comprises a transition metal.

[0150] Embodiment 15: 15. The process of any one of embodiments 12 to 14, wherein for the post-polymerization step, at least one hydroperoxide and at least one sulfite salt are used.

[0151] Embodiment 16: 16. The process of embodiment 15, wherein at least 5% of the total amount of hydroperoxide added is added after completion of sulfite addition.

[0152] Embodiment 17: 17. The process according to any one of embodiments 12 to 16, wherein volatile components are removed using steam distillation, thermal distillation, vacuum distillation, gas stripping to reduce, preferably essentially remove, the residual amount of monomer M1 and reaction by-products to a level required or acceptable for the intended area of ​​application, such steps being carried out at ambient pressure, reduced pressure or elevated pressure (up to 2 bar absolute), reducing the content of residual volatile monomers such as organic solvents, vinyl esters, etc. to a content of at most 1 percent by weight, preferably at most 0.5, more preferably at most 0.01%, based on the total weight of the obtained polymer dispersion.

[0153] Embodiment 18: 18. The process of any one of embodiments 12 to 17, wherein the dispersion is filtered to remove polymer aggregates greater than 125 micrometers in size.

[0154] Embodiment 19: Use of the aqueous polymer dispersion of embodiments 1 to 11 and / or the aqueous polymer dispersion obtainable or obtained by the process according to any one of embodiments 12 to 18 as an opacifying component.

[0155] Embodiment 20: The use according to embodiment 19 as an opacifying component in liquid and semi-liquid compositions in the field of cleaning compositions for use on fabrics and hard surfaces, for use in industrial and institutional cleaning.

[0156] Embodiment 21: 21. The use according to embodiment 19 or 20, wherein the composition additionally comprises at least one enzyme.

[0157] Embodiment 22: Use according to any one of embodiments 19 to 21 for imparting opacity.

[0158] Embodiment 23: 23. The use according to any one of embodiments 19 to 22, wherein the at least one aqueous polymer dispersion is present in a concentration of from about 0.01% to about 10% by weight (based on the solids content of the aqueous polymer dispersion), relative to the total weight of such composition or product.

[0159] Embodiment 24: 19. The use according to any one of embodiments 14 to 18, wherein such product or composition further comprises from about 1% to about 70% by weight of a surfactant system, and optionally further comprises at least one antimicrobial agent.

[0160] Embodiment 25: A liquid or semi-liquid formulation containing at least one aqueous polymer dispersion as defined in any one of embodiments 1 to 11, or an aqueous polymer dispersion obtainable or obtained according to any one of embodiments 12 to 18, in an amount of 0.01 to 10% (based on the solids content of the aqueous polymer dispersion), based on the total solids content of such formulation.

[0161] Embodiment 26: 26. The formulation of embodiment 25, which is a cleaning composition for use on fabrics and / or hard surfaces.

[0162] Embodiment 27: 27. The formulation of any of embodiments 25 or 26, which is a laundry detergent, cleaning composition or fabric and home care product containing at least one aqueous polymer dispersion to impart opacity.

[0163] Embodiment 28: 28. The formulation of any one of embodiments 25 to 27, further comprising from about 1% to about 70% by weight of a surfactant system, optionally comprising at least one antimicrobial agent and / or at least one enzyme.

[0164] Embodiment 29: 29. The formulation of any one of embodiments 25 to 28, further comprising 2-phenoxyethanol as an antimicrobial agent, preferably in an amount ranging from 2 ppm to 5%, more preferably from 0.1 to 2%, all by weight of the composition.

[0165] Embodiment 30: 30. The formulation according to any one of embodiments 25 to 29, further comprising 4,4'-dichloro 2-hydroxydiphenyl ether, each at a concentration of 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6% by weight of the composition.

[0166] Embodiment 31: 31. A method of protecting a formulation according to any one of claims 25 to 30 from microbial contamination or growth, the method comprising adding 2-phenoxyethanol as an antimicrobial agent to the composition, the composition being an aqueous composition comprising water as a solvent.

[0167] Embodiment 32: 30. A method for laundering fabrics or cleaning hard surfaces, comprising treating the fabrics or hard surfaces with the formulation according to any one of embodiments 25 to 29, comprising 4,4'-dichloro 2-hydroxydiphenyl ether, preferably 4,4'-dichloro 2-hydroxydiphenyl ether, respectively, at a concentration of 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6% by weight of the composition.

[0168] The following examples will further illustrate the invention without limiting its scope. [Example]

[0169] NTU value: See table for measurements with liquid detergent.

[0170] General Description of the Embodiments

[0171] [Table 7]

[0172] General Process Description 1. Precharge under nitrogen at 120 rpm to an internal temperature of 60 / 70°C 2. Add 5% Feed 1 in 1 minute at temperature and hold for 5 minutes 3. Start Feed 2 (4 hours 15 minutes) and Feed 3 (4 hours 15 minutes) 4. 15 minutes after Feed 2 and Feed 3 are started, the remainder of Feed 1 is started (3 hours 30 minutes) 5. At the end of Feed 2 and Feed 3, add Feed 4 (1 minute) and hold for 5 minutes. 6. Start of supply 5 (1 hour 30 minutes) 7. After Feed 5, hold for 30 minutes, then add Feed 6 (1 minute) 8. Hold for 30 minutes Cooled to an internal temperature of 9.23°C 10. Test with 125 μm filter while loading the filter

[0173] Device - 4L cylindrical glass reactor - V4A Round Anchor Stirrer - Weight supply module - heating bath

[0174] Detailed description of the general formula: At room temperature (23°C), an initial charge consisting of demineralized water, Finnfix 10 (carboxymethylcellulose) and sodium acetate as buffer is added to the reactor, after which the mixture is heated to 70°C with stirring under a N2 atmosphere. For Feed 1, demineralized water is mixed with demineralized water, Disponil FES 27, vinyl acetate and Visiomer C 18 PEG 1105 MA W. The feeds are mixed in a homogenizer to produce an emulsion. Add 70°C and 5% of Feed 1 in 1 minute. Then stir the mixture for 5 minutes. Then Feed 2, a 7% sodium persulfate solution, and Feed 3, a 2% ascorbic acid solution, are added at 4 hours and 30 minutes. After 30 minutes of Feeds 2 and 3, the remaining 95% of Feed 1 is added at 3 hours and 30 minutes. At the end of Feeds 2 and 3, stir for 10 minutes. Then, Feed 4, tert.-butyl hydroperoxide, is added in one shot, followed by Feed 5, 2.5% acetone sodium bisulfate solution, at 1 hour and 30 minutes for chemical deodorization. After Feed 5, cool to room temperature. Filter the final product through a 125 μm nylon filter.

[0175] [Table 8]

[0176] [Table 9]

[0177] [Table 10]

[0178] [Table 11]

[0179] Determination of opacity performance: Light transmittance (LD value) was determined photometrically at 525 nm in a 1 cm cuvette. Turbidity measurements were performed using a device from Hanna (Nephelometric Turbidimeter HI88703) to provide NTU values.

[0180] LD: (“Lichtdurchlaessigkeit” = light transmission): 1cm cuvette, 0.01% water; 525nm Particle size: Malver; D[0.5] 50% particles

[0181] Turbidity as a light scattering method: Nephelometric Turbidity Units (NTU); Formazine scale.

[0182] pH measurement: The dispersion is poured into a 250 ml beaker and the pH is measured at 25° C. by attaching a pH electrode (combined electrode) of a Knick Portamess meter. The measurement is carried out for 15 seconds until a constant pH value is reached.

[0183] Viscosity: Brookfield SP3, 250 rpm; 30% solids dispersion

Claims

1. below, a) an ethylenically unsaturated monomer M, (1) (M1) at least one vinyl ester, preferably comprising vinyl acetate, more preferably comprising at least 50% vinyl acetate; and (2) (M2) At least one (meth)acrylic acid ester, optionally containing methacrylic acid as a minor component, in which the (meth)acrylic acid in the methacrylic acid ester is linked via an ether function to a polyalkylene oxide derived block (PAO), the PAO consisting of 2 to 40 alkylene oxide (AO), most preferably 25 AO-units, the PAO preferably being linked via the ether function to a C1 to C24, preferably at least C4, more preferably at least C6, even more preferably C8 to C24-aliphatic alkanoate. alkane, most preferably a C18-aliphatic alkanol, wherein the AO is preferably selected from EO, PO and / or BuO, more preferably at least EO is present in an amount of from 50% by weight, more preferably at least 75% by weight, even more preferably at least 90% by weight, most preferably essentially EO only, based on the total AO; preferably comprising methacrylic acid, more preferably the methacrylic acid ester and free methacrylic acid are in a ratio of about 70% by weight / 30% to 80% by weight / 20% by weight, more preferably about 75% by weight / 25% by weight; (3) (M3) Optional further monomers (preferably absent) that are polymerizable with M1 and M2. an ethylenically unsaturated monomer M comprising: b) 1 to 15% by weight, preferably 2 to 10% by weight, based on the total weight of (CGCC) monomers M, of carboxyl group-containing compounds selected from compounds having at least three carboxyl groups in their structure, in which at least 10 percent and at most 90 percent of the carboxyl groups are deprotonated, such as citric acid, isocitric acid; ethylenediaminetetraacetic acid; nitriloacetic acid; tartaric acid; oligomeric and polyacrylic acids; oligomeric and polymethacrylic acids; trimellitic acid; oligomeric amino acids having carboxy groups, such as polyaspartic acid; oligomeric and polyglutamic acid; oligomeric and polyacetates having carboxy groups, such as poly(glyoxylic)aldehyde; oxidized starch (azathioprine); carboxylated oligomeric and polymeric sugars such as carboxylated celluloses (mixtures of cellulose, mylopectin, and amylose); polyglucuronates; celluloses oxidized to celluronates; natural polycarboxylic polysaccharides such as xylans; pectinic acid; alginic acid; carboxymethylated polysaccharides based on 1,4-, 1,3-, and 1,6-polyglucans; polyuronic acids based on 1,4-, 1,3-, and 1,6-polyglucans; polygalacturones; carboxyl group-containing compounds selected from the group comprising preferably carboxylated polysaccharides, more preferably carboxylated celluloses, and even more preferably carboxylated methylcellulose (carboxymethylcellulose, "CMC"); and c) (S) at least one non-carboxylated sugar and / or polysaccharide, such as glucose, starch degradation products, maltodextrin, in an amount of 2 to 50% by weight, preferably 5 to 35% by weight, based on the total weight of the monomers M; and d) at least one emulsifier selected from nonionic and anionic surfactants; e) optionally sulfate ions, and f) optionally sulfite ions 1. An aqueous polymer dispersion obtainable by radical aqueous emulsion polymerization of a mixture comprising Preferably, the amount of M1 is 80 to 99.99 mol %, the amount of M2 is 0.01 to 20 mol %, preferably at most 10, more preferably at most 5, more preferably at most 2%, the total amount of M1+M2 is 100 wt %; and The aqueous polymer dispersion, wherein the dispersion has a pH of at most 4 after completion of the polymerization.

2. (M1) the vinyl ester monomer comprises at least 50%, and even more preferably at least 90%, vinyl acetate, based on the total molar amount of vinyl esters; and (M2) the at least one (meth)acrylic acid ester is (meth)acrylic acid linked via an ether functional group to a polyalkylene oxide derived block (PAO), the PAO consisting of 20 to 30 alkylene oxide (AO), most preferably 25 AO units, the PAO preferably further linked via an ether functional group to a C14 to C22-aliphatic alkanol, most preferably a C16 / 18-aliphatic alkanol, the AO being selected from EO and PO and / or BuO, more preferably EO and PO, the EO being in an amount of from 75% by weight, more preferably at least 90% by weight, most preferably essentially EO only, based on the total AO; and further comprising methacrylic acid, the methacrylic acid ester and the free methacrylic acid being in a ratio of about 70% by weight / 30% to 80% by weight / 20% by weight, more preferably about 75% by weight / 25% by weight, and The dispersion of claim 1 , wherein (M3) is not included.

3. (M1) the vinyl ester monomer comprises at least 90% vinyl acetate, preferably essentially only vinyl acetate, based on the total molar amount of vinyl esters; and (M2) The dispersion of claim 2, wherein the at least one (meth)acrylic acid ester is (meth)acrylic acid linked via an ether functional group to a polyalkylene oxide derived block (PAO), the PAO consisting of 23 to 27 alkylene oxide (AO) units, most preferably an average of 25 AO units, the PAO being further linked via an ether functional group to an essentially C16 / 18-aliphatic alkanol, most preferably a C16 / 18-aliphatic alkanol, the AO consisting essentially of EO; and further comprising methacrylic acid, the methacrylic acid ester and the free methacrylic acid being in a ratio of about 70% / 30% to 80% / 20% by weight, more preferably about 75% / 25% by weight.

4. (M1) is vinyl acetate, and (M2) The dispersion of claim 3, wherein the at least one (meth)acrylic acid ester is methacrylic acid bonded to a polyethylene oxide block (PEO) via an ether functional group, the PEO consisting of an average of 25 AO units, the PEO further bonded to a C16 / 18-aliphatic alkanol via an ether functional group, and further comprising methacrylic acid, the methacrylic acid ester and the free methacrylic acid being in a ratio of about 75% by weight / 25% by weight.

5. 5. The dispersion of any one of claims 1 to 4, wherein said (CGCC) is a carboxyl group-containing compound selected from carboxylated polysaccharides, more preferably carboxylated celluloses, even more preferably carboxylated methyl cellulose (carboxymethyl cellulose, "CMC"), preferably in an amount of 2.5 to 10 wt. %, most preferably about 5 wt. %, based on the total amount of monomers (M1+M2+M3).

6. 6. The dispersion of any one of claims 1 to 5, wherein the dispersed polymer particles have a D[4,3] value determined by static light scattering of at least 400 and up to 1000 nm.

7. 7. Dispersion according to any one of claims 1 to 6, wherein (S) the at least one sugar and / or polysaccharide is a starch degradation product, preferably maltodextrin, in an amount of 10 to 30% by weight, preferably 15 to 25% by weight, more preferably 17 to 23% by weight, based on the total weight of the monomers M.

8. 8. The dispersion of claim 7, wherein (S) is a degraded starch having a dextrose equivalent according to Lane and Eynon in the range of 2-40%.

9. 9. The dispersion according to any one of claims 1 to 8, wherein as compound S a degraded starch is utilized having a number average molecular weight in the range of 300 to 2000 Daltons, determined by osmometry, preferably in the range of 5 to 150, more preferably at most 70, even more preferably at most 50, more preferably from 10, even more preferably from 15 and most preferably from 20, each in weight percent based on the total weight of the monomers (M1+M2+M3).

10. A method for producing a polymer dispersion according to any one of claims 1 to 9, comprising: A) an ethylenically unsaturated monomer M, (1) (M1) at least one vinyl ester, preferably comprising vinyl acetate, more preferably comprising at least 50%, even more preferably at least 90% vinyl acetate; and (2) (M2) At least one (meth)acrylic acid ester, optionally containing methacrylic acid as a minor component, in which the (meth)acrylic acid in the methacrylic acid ester is linked via an ether function to a polyalkylene oxide derived block (PAO), the PAO consisting of 2 to 40 alkylene oxide (AO), most preferably 25 AO-units, the PAO preferably being linked via the ether function to a C1 to C24, preferably at least C4, more preferably at least C6, even more preferably C8 to C24-aliphatic alkanoate. alkane, most preferably a C18-aliphatic alkanol, wherein the AO is preferably selected from EO, PO and / or BuO, more preferably at least EO is present in an amount of from 50% by weight, more preferably at least 75% by weight, even more preferably at least 90% by weight, most preferably essentially EO only, based on the total AO; preferably comprising methacrylic acid, more preferably the methacrylic acid ester and free methacrylic acid are in a ratio of about 70% by weight / 30% to 80% by weight / 20% by weight, more preferably about 75% by weight / 25% by weight; (3) (M3) Optional further monomers (preferably absent) that are polymerizable with M1 and M2. an ethylenically unsaturated monomer M comprising: at least one emulsifier, - water, - 1 to 15% by weight, preferably 2 to 10% by weight, more preferably 3 to 8% by weight, most preferably 4 to 6% by weight, based on the total weight of the (CGCC) monomers M, of carboxyl group-containing compounds selected from compounds having at least 3, more preferably at least 6, 8, 10, 15, 20, 25 or more carboxyl groups in their structure, in which at least 10 percent and at most 90 percent of the carboxyl groups are deprotonated and therefore form salts with counterions selected from Na, K, NH4, Mg, Ca, and from citric acid, isocitric acid; ethylenediaminetetraacetic acid; nitriloacetic acid; tartaric acid; oligomeric and polyacrylic acids; oligomeric and polymethacrylic acids; trimellitic acid; oligomeric amino acids containing carboxy groups, such as polyaspartic acid; oligomeric and polyglutamic acid; poly carboxylated oligomers and polyacetates such as (glyoxylic) aldehyde; carboxylated oligomeric and polymeric sugars such as oxidized starches, e.g., amylopectin, a mixture of amylose; polyglucronates; cellulose oxidized to celluronate; natural polycarboxylic polysaccharides such as xylan; pectinic acid; alginic acid; carboxymethylated polysaccharides based on 1,4-, 1,3-, and 1,6-polyglucans; polyuronic acids based on 1,4-, 1,3-, and 1,6-polyglucans; polygalacturons; carboxyl-containing compounds selected from the group including preferably carboxylated polysaccharides, more preferably carboxylated cellulose, and even more preferably carboxylated methylcellulose (carboxymethylcellulose, "CMC"); and (S) at least one non-carboxylated sugar and / or polysaccharide, such as glucose, starch degradation products, maltodextrin, in an amount of 2 to 50% by weight, preferably 5 to 35% by weight, more preferably 10 to 30% by weight, most preferably 15 to 25% by weight, based on the total weight of the monomer M; In the presence of polymerizing using at least one radical initiator, or preferably a peroxide and a reducing compound, more preferably a radical initiator pair comprising at least one persulfate and ascorbic acid and / or isoascorbic acid as radical polymerization initiators; Such polymerization is - in a reaction vessel equipped with either a pressure device and / or a device for controlling the boiling of the components, by which means the components can be contained in the reaction vessel during reaction at high temperature; at a temperature of 60 to 90, preferably 70 to 80°C; at a pH of at most 4, more preferably below 4, even more preferably at most 3.8, even more preferably at most 3.6 The steps to be performed; Furthermore B) optionally adding additional radical initiator or initiator couple to further reduce the content of unreacted monomer and / or reduce the color of the resulting polymer dispersion; C) optionally adding at least one additional reducing compound to reduce the color of the resulting polymer dispersion; D) optionally adding at least one further additive that may be required or desired as an additional component into the resulting polymer dispersion; E) optionally carrying out a step of removing volatilizable compounds from the reaction mixture by using a distillation step and / or a stripping step using steam or gas, preferably steam; F) optionally filtering the polymer dispersion from the previous step, preferably using a 125 micrometer filter; wherein the polymer dispersion is obtained.

11. The method of claim 10 , wherein the radical polymerization initiator additionally comprises a transition metal.

12. 12. The method according to any one of claims 10 to 11, wherein for the post-polymerization step at least one hydroperoxide and at least one sulfite salt are used.

13. 13. The method of claim 12, wherein at least 5% of the total amount of hydroperoxide added is added after completion of the sulfite addition.

14. Use of an aqueous polymer dispersion according to claims 1 to 9 or an aqueous polymer dispersion obtainable or obtained by the method according to any one of claims 10 to 13 as an opacifying component, preferably in liquid and semi-liquid compositions in the field of cleaning compositions for use on fabrics and hard surfaces, for use in industrial and institutional cleaning, wherein said at least one aqueous polymer dispersion is present in a concentration of from about 0.01% to about 10% by weight (based on the solids content of the aqueous polymer dispersion) based on the total weight of such composition or product; Preferably, the composition meets the following requirements: a. preferably comprising at least one enzyme selected from one or more lipases, hydrolases, amylases, proteases, cellulases, mannanases, hemicellulases, phospholipases, esterases, xylanases, DNases, dispersins, pectinases, oxidoreductases, cutinases, lactases, and peroxidases, more preferably at least two of said species, and if an enzyme is included, preferably also comprising at least one enzyme stabilizing system; b. comprising from about 1% to about 70% by weight of a surfactant system; c. comprising an effective amount of at least one additional cleaning adjunct; and d. preferably exhibiting improved cleaning performance in primary cleaning The use further satisfies at least one of the above.

15. 15. A liquid or semi-liquid formulation containing at least one aqueous polymer dispersion as defined in any one of claims 1 to 9 or an aqueous polymer dispersion obtainable or obtained according to any one of claims 10 to 14 in an amount of 0.01 to 10% (based on the solids content of said aqueous polymer dispersion), based on the total solids content of such formulation, Optionally, a) to c) a. at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, mannanases, hemicellulases, phospholipases, esterases, xylanases, DNases, dispersins, pectinases, oxidoreductases, cutinases, lactases, and peroxidases, more preferably at least two of said species (if an enzyme is included, preferably also at least one enzyme stabilizing system); b. about 1% to about 70% by weight of a surfactant system; c. an effective amount of at least one additional cleaning adjunct and further comprising at least one of Preferably it is a cleaning composition or a fabric and home care product, more preferably a cleaning composition, more preferably a laundry detergent or a dishwashing detergent; Even more preferably it is a concentrated liquid detergent formulation, a single dose laundry detergent formulation, a liquid hand dishwashing detergent formulation, most preferably a liquid laundry detergent formulation or a liquid hand dishwashing detergent formulation; optionally further comprising at least one antimicrobial agent, preferably 2-phenoxyethanol, in an amount of from 2 ppm to 5%, more preferably from 0.1 to 2%, by weight of the composition; Optionally, a liquid or semi-liquid formulation comprising 4,4'-dichloro 2-hydroxydiphenyl ether at a concentration of 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6%, each based on the weight of the composition.

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