Aqueous polymer dispersions suitable as opacifiers in liquid formulations, methods of production and uses thereof

Abstract

The present invention relates to aqueous polymer dispersions suitable as opacifiers in liquid formulations, to methods of production, to the use of such aqueous polymer dispersions in cleaning compositions and to such compositions. These aqueous polymer dispersions are obtainable by free-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 comprise methacrylic acid as a secondary component, the (meth) acrylic acid in the methacrylate is bonded to a polyalkylene oxide-derived block (PAO) via an ether function wherein the PAO consists of (2) to (40) alkylene oxides (AO), iii) optionally further polymerizable monomers, the polymerization being in the presence of: a) carboxyl group-containing compounds selected from compounds having at least three carboxyl groups in the structure thereof, and b) optionally further polymerizable monomers selected from the group consisting of compounds having at least three carboxyl groups in the structure thereof; wherein at least (10) and at most (90) percent 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 further containing sulfate ions and / or sulfite ions.

Description

[0001] The present invention relates to an aqueous polymer dispersion which is suitable as an emulsifier in liquid formulations.

[0002] The present invention further relates to an aqueous polymer dispersion obtainable by free radical emulsion polymerization in an aqueous medium by polymerizing: i) at least one vinyl ester, ii) at least one (meth)acrylate which may optionally contain methacrylic acid as a minor component, wherein the (meth)acrylic acid in the methacrylate is bonded via an ether functional group to a polyalkylene oxide-derived block (PAO), where PAO consists of 2 to 40 alkylene oxides (AO), iii) optionally further polymerizable monomers, the polymerization being in the presence of: a) a carboxyl-containing compound selected from compounds having at least three carboxyl groups in their structure, wherein at least 10 and at most 90 percent 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 further containing sulfate ions and / or sulfite ions. Also covered is the use of such aqueous polymer dispersions in cleaning compositions such as detergents, including the use of the aqueous polymer dispersion as an emulsifier.

[0003] The present invention also relates to formulations and compositions in the fields of fabric and home care, industrial and institutional cleaning applications which comprise at least one aqueous polymer dispersion as disclosed herein.

[0004] Due to climate change, one of the most important goals of the detergent and cleaning (D&C) industry today is to significantly reduce the CO2 emissions per wash by, for example, improving the cleaning efficiency under cold water conditions (by improving the cleaning efficiency at temperatures below 40, 30 or 20 or even lower), thereby reducing the amount of chemicals used per wash, increasing the weight efficiency of cleaning technologies, reducing the amount of water per wash, introducing bio-derived components, etc. Thus, an important goal of the D&C industry is to improve the sustainability of cleaning formulations by improving efficiency (especially still at lower temperatures), requiring less water (especially still in laundry formulations and dishwashing formulations) and avoiding the accumulation of non-degradable compounds in the ecosystem. This reduction in CO2 emissions or the hope of improving the "footprint" of any product is of high and even further increasing interest in industry as well as for consumers, whether its source is like from natural or renewable resources, or all in comparison with previous products - in terms of its production efficiency and thus reduced energy use, its use efficiency such as reduced amount for the same performance or improved performance at the same usage level, its persistence in the natural environment during and / or after its use such as biodegradability.

[0005] Due to these trends, there is a strong need for new biodegradable cleaning additives that provide at least comparable cleaning properties and a reduced CO2 footprint due to being bio-derived, biodegradable, or both. These materials should preferably exhibit good primary cleaning activity, detergency against oily / fatty and particulate stains, and / or should result in improved whiteness retention, thereby also minimizing the amount of suspended and emulsified oily / fatty and particulate stains from redepositing on textile surfaces or hard surfaces, etc.

[0006] Accordingly, there is a need to provide compounds that are biodegradable and still have at least the same performance as known but non-biodegradable compounds, such as biodegradation measured within 28 days under specified conditions, which is required by many users, especially in the detergent field, and is required by applicable legislation in several countries and regions of the world in the future. Background Art

[0007] Emulsifiers of the prior art are based on styrene / methacrylic acid copolymers produced by emulsion polymerization. They are widely used in household care and personal care products. The drawback is the lack of biodegradability. In addition, current production methods are subject to reactor fouling and a large amount of condensate, which reduces the total capacity in commercial equipment.

[0008] D1 (EP1924633, BASF) claims a process and a dispersion consisting of vinyl acetate and 0.05% - 5.0% by weight of methacrylic acid, which are obtained by free-radical-initiated emulsion polymerization. The particle size is determined to be 100 - 200 nm. A protective colloid (Kollidon 30, polyvinylpyrrolidone K30) is used and sodium dodecyl sulfate is used as an emulsifier. The target applications are film coating in pharmacological and cosmetic applications and slow release of active ingredients. Biodegradation results are not published. The use of polycarboxylates such as carboxymethyl cellulose to improve biodegradation is not disclosed.

[0009] D2 (DE102004031970, Wacker) describes a process consisting of vinyl monomers such as vinyl acetate and ethylenically unsaturated polyethers such as allyl polyethers and solution polymerization in methanol. Also claimed are esters of polyethers corresponding to methacrylic acid having terminal groups OH and OR, where R can be an alkyl group having C1 - C40. The target application is for producing plasticized vinyl acetate solid resins. Biodegradation results are not published. The use of polycarboxylates such as carboxymethyl cellulose to improve biodegradation is not disclosed.

[0010] In D3 (JP2005089540, Konishi), a vinyl acetate polymer resin is produced by an emulsion method in the presence of a polymerizable polyethylene glycol derivative. The use of a cellulose-based protective colloid is reported. The target applications are for adhesives, film formation, fibers and paper coatings, and binders in paper processing. Biodegradation results are not published. The use of polycarboxylates such as carboxymethyl cellulose to improve biodegradation is not disclosed.

[0011] In D4 (JP06093007, Aica Kogyo, JP1992-269400), an emulsion based on polyvinyl acetate is reported, in which 50%-100% by weight of vinyl acetate and 0%-50% by weight of one or more comonomers (such as acrylates) are subjected to emulsion polymerization by using a water-soluble modified starch (such as esterified starch or etherified starch) as a protective colloid at 10%-200% by weight based on the total monomers. The target application is for producing films with good low-temperature properties and high hardness. Biodegradation results are not published. The use of polycarboxylates such as carboxymethyl cellulose to improve biodegradation is not disclosed.

[0012] D5 (US4708999, Celanese, Air Products & Chemicals, US1986-894419) describes the solution polymerization of vinyl acetate and C1 to C12 alkyl polyethylene glycol methacrylate (polyethylene glycol with 25 ethylene oxides) in methanol. The product is then subjected to methanolysis. The amount of methacrylate given in the examples is 0.56 to 1.85 mol%, and claim 1 includes 0.001 - 50 mol%. The molecular weights in the examples are given as being between 36,000 and 77,000 g / mol. Biodegradation results are not published. The use of polycarboxylates such as carboxymethyl cellulose to improve biodegradation is not disclosed.

[0013] In D6 (JP59155411, NIPPON SYNTHETIC CHEM., JP1983 - 028686), copolymers in the solution polymerization of an unsaturated monomer containing an oxyalkylene and vinyl acetate in an alcohol are described. The copolymerization of vinyl acetate with an unsaturated monomer containing an oxyalkylene (such as methacrylic acid) … The number of oxyalkylenes, i.e., n, is advantageously from 1 to 50 and preferably about 3 to 50. The ends of the oxyalkylenes can be alkyl groups. Examples preferably include allyl polyoxyethylene, and an example is (10EO)-oxyethylene methacrylate. A modified vinyl acetate resin is applied, which is water-soluble even in the absence of alkali metals and is suitable for use as a paste, adhesive, or aqueous solution in paper processing. No biodegradation results are published. The use of polycarboxylates such as carboxymethyl cellulose to improve biodegradation is not disclosed.

[0014] D7 (US3322703, Cumberland Chemical) claims a copolymer composed of an alkoxypolyalkylene glycol half - ester of vinyl acetate and an unsaturated dicarboxylic acid or / and an alkoxypolyalkylene glycol ester of vinyl acetate and an unsaturated monocarboxylic acid, and a preparation method. As an example, the solution polymerization of vinyl acetate and methoxypolyethylene glycol maleate in methanol is given. No use is claimed, but it is described in the form of the application of sized articles, which can be wetted and form a sticky film, for example, for stamps. No biodegradation results are published. The use of polycarboxylates such as carboxymethyl cellulose to improve biodegradation is not disclosed.

[0015] In D8 (EP199358 of Celanese Corp), a terpolymer composed of vinyl alcohol, vinyl acetate, and alkyl polyoxyethylene methacrylate is claimed. Fabric protection includes at least 50% vinyl alcohol in the terpolymer. The use of the terpolymer as a barrier layer in a thermoplastic process for packaging articles. No biodegradation results are published. The use of polycarboxylates such as carboxymethyl cellulose to improve biodegradation is not disclosed.

[0016] Purpose

[0017] Due to climate change, one of the most important goals of the current detergents and cleaning (D&C) industry is to significantly reduce the CO2 emissions per wash by, for example, improving the cleaning efficiency under cold water conditions (by improving the cleaning efficiency at low temperatures below 40, 30 or 20 or even lower), thereby reducing the amount of chemicals used per wash, increasing the weight efficiency of cleaning technologies, introducing bio-derived components, etc. Thus, an important goal of the D&C industry is the demand for biodegradable ingredients to improve the sustainability of cleaning formulations (and especially laundry and dishwashing formulations) and to avoid the accumulation of non-degradable compounds in the ecosystem. Therefore, there is a need to provide compounds that are biodegradable and still have at least the same performance as known but non-biodegradable compounds, such as biodegradation measured within 28 days under defined conditions, which is required by many users, especially in the detergent field, and is required by applicable legislation in several countries and regions of the world in the future.

[0018] This hope of reducing CO2 emissions or improving the "footprint" of any product has a high and even further increasing interest in the industry as well as for consumers, whether its source is from natural or renewable resources, or all in comparison to previous products - in terms of its production in terms of production efficiency and thus reduced energy use, its use efficiency such as reduced amount at the same performance or improved performance at the same usage level, its persistence in the natural environment during and / or after its use such as in terms of biodegradation.

[0019] Due to these trends, there is a strong need for new biodegradable cleaning additives that provide at least comparable cleaning properties and a reduced CO2 footprint due to being bio-derived, biodegradable or even both. These materials should preferably exhibit good primary cleaning activity, detergency against oily / fatty and particulate stains, and / or should result in improved whiteness retention, minimizing the amount of suspended and emulsified oily / fatty and particulate stains to avoid redeposition on textile surfaces or hard surfaces, etc.

[0020] Therefore, the aim is to provide an emulsifier for compositions such as detergents, cleaning and / or fabric and home care compositions / formulations with improved biodegradability.

[0021] This aim is solved by an aqueous dispersion as defined herein, a method for producing such a dispersion, and its use and a composition comprising such a dispersion.

[0022] The aqueous dispersion of the invention obtainable or obtained by the method according to the invention can be used as an emulsifier in specific compositions such as detergents, cleaning and / or fabric and home care compositions / formulations.

[0023] Definitions

[0024] Unless otherwise expressly defined hereinbelow or throughout this specification, all terms have their ordinary meaning.

[0025] Throughout this specification and the following claims, unless the context requires otherwise, the word "comprise" and variations such as "comprises" and "comprising" will be understood to mean including the stated integer or step or group of integers or steps but not excluding any other integer or step or group of integers or steps. When used herein, the term "comprising" may be replaced by the term "containing" or "including", or sometimes when used herein by the term "having".

[0026] When used herein, "consisting of" excludes any element, step or ingredient not specified in the claim. When used herein, "consisting essentially of" does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim.

[0027] In each case herein, any one of the terms "comprise", "consisting essentially of" and "consisting of" may be replaced by any one of the other two terms. In a preferred embodiment, "comprising" may be replaced by "consisting essentially of", and in an even more preferred embodiment, both may be replaced by "consisting of".

[0028] The compositions of the present disclosure may "comprise" the components of the present disclosure (i.e., contain other ingredients), "consist essentially of the components of the present disclosure" (primarily or almost exclusively containing the ingredients mentioned and only very small amounts of other ingredients that are primarily only impurities) or "consist of the components of the present disclosure" (i.e., contain only the ingredients mentioned and may additionally contain only impurities that are unavoidable in the technical environment, preferably only these ingredients).

[0029] Similarly, the present disclosure may use the terms "substantially free of" or "substantially free from" or "substantially not (containing / including) ..."; this means that the indicated material is present in a very small amount that is not intentionally added to the composition to form a part thereof, or, preferably, is not present at an analytically detectable level. It means including compositions in which the indicated material is present only as an impurity in one of the other materials intentionally included. If present at all, the indicated material may be present at a level of less than 1%, or even less than 0.1%, or even much less than 0.01%, or even 0% by weight of the composition.

[0030] Generally, as used herein, the term "obtainable by" means that the corresponding product does not necessarily have to be produced (i.e., obtained) by the corresponding method or process described in the corresponding specific context, but also includes products that exhibit all the characteristics of products produced (obtained) by the said corresponding method or process, where the product is not actually produced (obtained) by such method or process. However, the term "obtainable by" also includes the more restrictive term "obtained by", i.e., products actually produced (obtained) by the method or process described in the corresponding specific context.

[0031] When using any definition in this disclosure that requires a compound or a substituent of a compound to consist of "at least a plurality 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, for a substituent disclosed as an "alkyl ether having at least 8 carbon atoms containing an epoxyalkyl group", the total number of at least 8 carbon atoms needs to be the sum of the number of carbon atoms in the alkyl part and the number of carbon atoms in the epoxyalkane part.

[0032] All such terms not specifically defined have their ordinary meanings as known in the field of organic chemistry.

[0033] As used herein, when used in claims or examples, the articles "a" and "an" shall be understood to mean one or more of what is claimed or described. As used herein, the terms "include" and "including" are meant to be non-restrictive and thus cover more than the specific item(s) mentioned after these words.

[0034] As used herein, the term "about" encompasses the exact numerical value "X" being referred to, e.g., "about X %", etc., as well as small variations of X, including deviations from X - 5% to +5% (for this calculation, X is set to 100%), preferably -2% to +2%, more preferably -1% to +1%, even more preferably -0.5% to +0.5% and even smaller variations. Of course, if the given value X itself is already "100%" (such as for purity, etc.), then the term "about" obviously can and thus only means a deviation less than "100".

[0035] The term "water - free" means that the composition contains no more than 5 wt.-% water based on the total amount of the solvent, in another embodiment no more than 1 wt.-% water based on the total amount of the solvent, and in another embodiment, the solvent contains no water at all.

[0036] Unless otherwise indicated, all temperatures herein are in degrees Celsius (°C). Unless otherwise specified, all measurements herein are made at 20 °C and at atmospheric pressure. In all embodiments of this disclosure, unless otherwise specifically stated, all percentages are by weight of the total composition. Unless otherwise specifically stated, all ratios are weight ratios.

[0037] The phrase "fabric care composition" means compositions and formulations designed to be used for treating fabrics. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric strengthening compositions, fabric brightening compositions, laundry pre - washes, laundry pre - treatments, laundry additives, spray products, dry - cleaning agents or compositions, laundry rinse additives, wash additives, post - rinse fabric treatments, ironing aids, unit - dose formulations, delayed - delivery formulations, detergents contained on or in porous substrates or non - woven sheets, and other suitable forms that would be obvious to a person skilled in the art in view of the teachings herein and are detailed below when describing the compositions. Such compositions can be used as pre - wash treatments, post - wash treatments, or can be added during the rinse or wash cycle of a washing operation, and are further detailed below when describing the uses and applications of the present invention and compositions containing such dispersions of the present invention.

[0038] Molecular weight descriptors Mw, Mn and the polydispersity of the molecular weight (PDI is the polydispersity index); pH value.

[0039] Unless otherwise explicitly defined, all given percentages are weight percentages based on the total weight of the composition, dispersion, feed, mixture, etc.; abbreviated as "wt %".

[0040] "Biodegradable" and "biodegradation", whether or not qualified by "as tested under standard conditions", mean biodegradation of the substance, compound or formulation mentioned, and – if a percentage is given, such as "30% biodegradable / biodegradation" – this is determined by a biodegradability test in accordance with OECD 301F (as used in the Examples section).

[0041] "Median particle size" and the corresponding "median particle size measurement" mean the particle size D[4,3] measured in an aqueous environment using standard methods and components, such as with a Malvern Mastersizer 2000. The Mastersizer used for the present invention is equipped with a Hydro 2000S(a) as an accessory, using water as the dispersant at a concentration of 0.0220 volume percent.

[0042] "Transmittance of light at a wavelength of 532 nm" means the transmittance measured with light at a wavelength of 532 nm using a standard machine, such as preferably a Hach Lange DR6000 spectrometer, compared to the transmittance of a standard, which is usually white water suitable for such measurements, preferably distilled water or even double distilled water, at a concentration of 0.01 wt.%, and a cuvette with a 1 cm dispersion length for the light to pass through.

[0043] pH measurements are carried out as described in the experimental section.

[0044] Throughout the present specification, the term "compounds of the invention" may be used in place of "aqueous dispersions of the invention" and "aqueous dispersions of the present (current) invention", meaning those compounds disclosed as an invention herein, defined by their structure and / or their production method and / or obtainable by the methods defined herein. Detailed Description

[0045] As described below, the definitions given in the preceding "Definitions" section and their preferred options are included as part of the present invention.

[0046] The present invention encompasses the specific embodiments described throughout this disclosure as part of the present invention; various additional options are disclosed in the present invention specification as "optional", "preferred", "more preferred", "even more preferred" or "most preferred" (or "preferably", etc.), and the options of the specific embodiments can be selected individually and independently (unless such independent selection is impossible due to the nature of the feature or if such independent selection is expressly excluded) and then combined with any other embodiment (where other such options and preferred options can also be selected individually and independently, unless such independent selection is impossible due to the nature of the feature or if such independent selection is expressly excluded), where each and any and all such possible combinations are included as separate embodiments as part of the present invention.

[0047] Specifically, the present invention relates to an aqueous polymer dispersion obtainable by free radical aqueous emulsion polymerization of a mixture comprising

[0048] a) ethylenically unsaturated monomers M, where M comprises

[0049] (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

[0050] (2) (M2) at least one (meth)acrylate optionally comprising methacrylic acid as a minor component, wherein the (meth)acrylic acid in the methacrylate is bonded via an ether functional group to a block (PAO) derived from a polyalkylene oxide, where the PAO consists of 2 to 40 alkylene oxide (AO) units, most preferably 25 AO units, where the PAO is preferably further linked via an 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 C18 - aliphatic alkanol, where the AO is preferably selected from EO, PO and / or BuO, more preferably at least EO, in an amount of 50, more preferably at least 75, even more preferably at least 90 wt.%, most preferably substantially only EO, based on the total AO; preferably comprising methacrylic acid, more preferably where the ratio of the methacrylate and the free methacrylic acid is about 70 w% / 30 w% to 80 w% / 20 w%, more preferably about 75 w% / 25 w%;

[0051] (3) (M3) optionally additional monomers copolymerizable with M1 and M2, preferably none;

[0052] b) (CGCC) carboxyl-containing compounds in an amount of 1 to 15, preferably 2 to 10, more preferably 3 to 8, and most preferably 4 to 6% by weight, based on the total weight of monomer M, said compounds being selected from compounds having at least three, more preferably at least 6, 8, 10, 15, 20, 25 or more carboxyl groups in their structure, wherein at least 10 and at most 90 percent are deprotonated (thus forming salts with counterions; these counterions are selected from Na, K, NH4, Mg, Ca), and being selected from the group comprising: citric acid, isocitric acid; ethylenediaminetetraacetic acid; nitrilotriacetic acid; tartaric acid; oligomeric and polyacrylic acids; oligomeric and polymethacrylic acids; trimellitic acid; oligomeric amino acids having carboxyl groups, such as polyaspartic acid; oligomeric and polyglutamic acids; oligomeric and polyacetates having carboxyl groups, such as poly(glyoxylic acid) aldehyde; carboxylated oligomeric and polysaccharides, such as oxidized starch (a mixture of amylopectin, amylose); polyglucuronate; cellulose oxidized to fibroglucuronic acid; natural polycarboxylic polysaccharides, such as xylan gum; pectic acid; alginic acid; carboxymethylated polysaccharides based on 1,4-glucan, 1,3-glucan, 1,6-glucan; glycuronans based on 1,4-glucan, 1,3-glucan, 1,6-glucan; polygalacturonic acid; preferably carboxylated polysaccharides, more preferably carboxylated cellulose, and even more preferably carboxymethyl cellulose (carboxymethyl cellulose, "CMC"); and

[0053] 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, preferably 5 to 35, more preferably 10 to 30, and most preferably 15 to 25 wt% based on the total weight of monomer M,

[0054] and

[0055] d) at least one emulsifier selected from nonionic and anionic surfactants, wherein

[0056] i) said at least one ionic surfactant is selected from:

[0057] anionic emulsifiers having at least one anion group selected from phosphate, phosphonate, sulfate and sulfonate groups;

[0058] said anionic emulsifier is typically used in the form of its alkali metal salt (especially its sodium salt) or in the form of its ammonium salt;

[0059] preferably, said anionic emulsifier has at least one sulfate or sulfonate group or at least one phosphate or phosphonate group, more preferably has at least one sulfonate or sulfate group, and most preferably has only one sulfonate or one sulfate group,

[0060] i)a) wherein said anionic emulsifier having at least one sulfate or sulfonate group is preferably selected from

[0061] - Salts of alkyl sulfates, especially C8-C22-alkyl sulfates, especially alkali metal salts and ammonium salts,

[0062] - Salts of monoesters of sulfuric acid of C2-C3-alkoxylated alkanols, especially monoesters of sulfuric acid of C2-C3-alkoxylated C8-C22-alkanols (preferably having a C2-C3-alkoxylation level (AO level) in the range from 2 to 40), especially alkali metal salts and ammonium salts,

[0063] - Salts of monoesters of sulfuric acid of C2-C3-alkoxylated alkylphenols, especially monoesters of sulfuric acid of C2-C3-alkoxylated C4-C18-alkylphenols (AO level preferably 3 to 40), especially alkali metal salts and ammonium salts,

[0064] - Salts of alkylsulfonic acids, especially C8-C22-alkylsulfonic acids, especially alkali metal salts and ammonium salts,

[0065] - Salts of dialkyl esters of sulfosuccinic acid, especially di-C4-C18-alkyl esters, especially alkali metal salts and ammonium salts,

[0066] - Salts of alkylbenzenesulfonic acids, especially C4-C22-alkylbenzenesulfonic acids, especially alkali metal salts and ammonium salts, and

[0067] - Mono- or disulfonated alkyl-substituted diphenyl ethers, such as salts of bis(benzenesulfonic acid) ethers carrying C4-C24-alkyl groups on one or both aromatic rings, especially alkali metal salts and ammonium salts;

[0068] The term "C2-C3-alkoxylated" means that these compounds are ethoxylated, propoxylated or co-ethoxylated / propoxylated, i.e. it means that the corresponding compounds are obtained by the method of introducing poly(ethylene oxide) groups, poly(propylene oxide) groups or poly(ethylene oxide - co - propylene oxide) groups;

[0069] i) b) wherein the anionic emulsifier carrying at least one phosphate or phosphonate group is preferably selected from

[0070] - Salts of mono- and dialkyl phosphates, especially C8-C22-alkyl phosphates, especially alkali metal salts and ammonium salts,

[0071] - Mono - phosphates of C2 - C3 - alkoxylated alkanols (preferably having an alkoxylation level in the range from 2 to 40, especially in the range from 3 to 30), such as mono - phosphates of ethoxylated C8 - C22 - alkanols (preferably having an ethoxylation level (EO level) in the range from 2 to 40), mono - phosphates of propoxylated C8 - C22 - alkanols (preferably having a propoxylation level (PO level) in the range from 2 to 40), and salts of mono - phosphates 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 from 1 to 20), especially alkali metal salts and ammonium salts,

[0072] - Salts of mono - phosphates of C2 - C3 - alkoxylated alkylphenols, especially salts of mono - phosphates of C2 - C3 - alkoxylated C4 - C18 - alkylphenols (AO level preferably 3 to 40), especially alkali metal salts and ammonium salts,

[0073] - Salts of alkylphosphonic acids, especially C8 - C22 - alkylphosphonic acids, especially alkali metal salts and ammonium salts, and

[0074] - Salts of alkylbenzenephosphonic acids, especially C4 - C22 - alkylbenzenephosphonic acids, especially alkali metal salts and ammonium salts;

[0075] Wherein more preferred anionic emulsifiers are selected from the group consisting of:

[0076] - Salts of alkyl sulfates, especially salts of C8 - C22 - alkyl sulfates, especially alkali metal salts and ammonium salts,

[0077] - Mono - sulfates of C2 - C3 - alkoxylated alkanols, especially salts of mono - sulfates of C2 - C3 - alkoxylated C8 - C22 - alkanols (preferably having an AO level in the range from 2 to 40), especially alkali metal salts,

[0078] - Mono - sulfates of C2 - C3 - alkoxylated alkylphenols, especially mono - sulfates of C2 - C3 - alkoxylated C4 - C18 - alkylphenols (AO level preferably 3 to 40),

[0079] - Alkylbenzenesulfonic acids, especially C4 - C22 - alkylbenzenesulfonic acids, and

[0080] - Mono - or disulfonated alkyl - substituted diphenyl ethers, such as bis(benzenesulfonic acid) ethers bearing C4 - C24 - alkyl groups on one or both aromatic rings;

[0081] ii) The at least one non - ionic surfactant is selected from:

[0082] The non - ionic emulsifier is for example an araliphatic or aliphatic non - ionic emulsifier selected from the following

[0083] -C2-C3-alkoxylated mono-, di- and tri-alkylphenols, wherein the number of repeating units of the alkylene oxide-derived moiety is preferably from 3 to 50, and / or the alkyl is preferably a C4-C10-alkyl;

[0084] -C2-C3-alkoxylates of long-chain alcohols, such as ethoxylates, propoxylates or ethoxylate-copropoxylates, wherein the number of repeating units of the alkylene oxide-derived moiety is preferably from 3 to 100, and / or the alkyl is preferably a C8-C36-alkyl, and

[0085] -polyethylene oxide / polypropylene oxide homopolymers and copolymers, which may comprise alkylene oxide units copolymerized in a random distribution or in the form of blocks or mixtures of homopolymeric blocks and random blocks,

[0086] more preferably the C2-C3-alkoxylation of long-chain alkanols, especially those having an average alkoxylation level of 5 to 100 for an alkyl C8-C30, and among these, particularly preferably those having a straight-chain C12-C20 alkyl and an average alkoxylation level of 10 to 50, and also C2-C3-alkoxylated mono-alkylphenols;

[0087] and

[0088] e) optionally sulfate ions, and

[0089] f) optionally sulfite ions,

[0090] wherein – preferably – the amount of M1 is 80 to 99.99 mol%, more preferably the amount of M1 is at least 98%, and the amount of M2 is 0.01 to 20 mol%, more preferably 0.1, even more preferably 0.2, even more preferably 0.5, and most preferably 0.7, and preferably at most 10, even more preferably at most 5, more preferably at most 2, and most preferably, the amount of M1 is about 99 weight percent and the amount of M2 is about 1 weight percent, the total amount of M1 plus M2 is 100 weight percent, and

[0091] wherein the dispersion has – after the end of the polymerization – a pH of up to 4, more preferably below 4, even more preferably at most 3.8, even more preferably at most 3.6, and 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.

[0092] In a preferred embodiment 2 of the aqueous polymer dispersion as defined above, (M1) the 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.

[0093] In another preferred embodiment 3, (M2) the at least one (meth)acrylate is (meth)acrylic acid bonded to a polyalkylene oxide-derived block (PAO) via an ether functionality, where the PAO consists of 20 to 30 alkylene oxide (AO) units, most preferably 25 AO units, where the PAO is preferably further linked via an ether functionality to a C14 to C22-aliphatic alkanol, most preferably a C16 / 18-aliphatic alkanol, where the AO is selected from EO and PO and / or BuO, more preferably EO and PO, where based on the total AO, the amount of EO is 75, even more preferably at least 90 wt.%, most preferably essentially only EO; further comprising methacrylic acid, where the ratio of the methacrylate and the free methacrylic acid is from about 70 w% / 30 w% to 80 w% / 20 w%, or preferably about 75 w% / 25 w%.

[0094] In another preferred embodiment 4, (M3) is not comprised.

[0095] In an even more preferred embodiment 5 of the aqueous polymer dispersion as defined previously, (M1) the vinyl ester monomer comprises at least 50%, even more preferably at least 90% of vinyl acetate, based on the total molar amount of vinyl ester.

[0096] (M2) the at least one (meth)acrylate is (meth)acrylic acid bonded to a polyalkylene oxide-derived block (PAO) via an ether functionality, where the PAO consists of 20 to 30 alkylene oxide (AO) units, most preferably 25 AO units, where the PAO is preferably further linked via an ether functionality to a C14 to C22-aliphatic alkanol, most preferably a C16 / 18-aliphatic alkanol, where the AO is selected from EO and PO and / or BuO, more preferably EO and PO, where based on the total AO, the amount of EO is 75, even more preferably at least 90 wt.%, most preferably essentially only EO; further comprising methacrylic acid, where the ratio of the methacrylate and the free methacrylic acid is from about 70 w% / 30 w% to 80 w% / 20 w%, more preferably about 75 w% / 25 w%, and (M3) is not comprised.

[0097] In another more preferred embodiment 6, (M1) the vinyl ester monomer comprises at least 90% by mole of vinyl acetate, preferably substantially only vinyl acetate, based on the total molar amount of the vinyl ester, and (M2) the at least one (meth)acrylate is (meth)acrylic acid bonded to a polyalkylene oxide-derived block (PAO) via an ether functional group, wherein the PAO consists of 23 to 27 alkylene oxide (AO) units, most preferably an average of 25 AO units, wherein the PAO is preferably further linked via an ether functional group to a substantially C16 / 18-aliphatic alkanol, most preferably C16 / 18-aliphatic alkanol, wherein the AO is substantially only EO; further comprising methacrylic acid, wherein the ratio of the (meth)acrylate and the free methacrylic acid is from about 70 w% / 30 w% to 80 w% / 20 w%, more preferably about 75 w% / 25 w%, and (M3) is absent.

[0098] In another more preferred embodiment 7 of the aqueous polymer dispersion as defined above,

[0099] (M1) is vinyl acetate, and (M2) the at least one (meth)acrylate is (meth)acrylic acid bonded to a polyethylene oxide block (PEO) via an ether functional group, wherein the PEO consists of an average of 25 AO units, wherein the PEO is further linked via an ether functional group to a C16 / 18-aliphatic alkanol, further comprising methacrylic acid, wherein the ratio of the (meth)acrylate and the free methacrylic acid is about 75 w% / 25 w%, and (M3) is absent.

[0100] In another more preferred embodiment 8, and preferably in combination with any of the previous embodiments, the aqueous dispersion comprises a carboxyl-containing compound as (CGCC) selected from carboxylated polysaccharides, more preferably carboxylated cellulose, even more preferably carboxylated methylcellulose (carboxymethylcellulose, "CMC"), preferably in an amount of from 1 to 15 weight percent, more preferably up to 10, even more preferably up to 5 wt% and most preferably about 5 weight percent, based on the total amount of monomers (M1 + M2 + M3).

[0101] It is believed that the CGCC is capable of interacting with the polymerized moiety derived from at least one monomer M2 within the polymer product dispersed in the dispersion. Through such interaction, excellent compatibility and stability of the dispersion seem to be produced; moreover, such interactions facilitate the attack on the chemical structure and thus provide the observed high percentage of biodegradation of the aqueous polymer dispersion, which is higher than that of a dispersion without a carboxyl-containing compound (CGCC).

[0102] In a further preferred embodiment 9, and preferably in combination with any of the preceding embodiments, the aqueous polymer dispersion comprises (S) at least one sugar and / or polysaccharide which is a starch degradation product, preferably maltodextrin, in an amount of 10 to 30, most preferably 15 to 25 wt%, based on the total weight of monomers M.

[0103] In a preferred variant of this preceding embodiment 9, (S) is a degraded starch having a glucose equivalent in the range of 2 to 40% according to Lane and Eynon.

[0104] In a preferred variant of the two preceding embodiments, (S) is a maltodextrin having a DE-value of 10 to 30, preferably 12 to 16 or 25 to 30.

[0105] In a preferred variant of the two preceding embodiments 8 and 9, (S) is a degraded starch, as determined by osmometry, having a number average molecular weight in the range of 300 to 2000 daltons, and preferably in the range of 5 to 150, more preferably up to 70, even more preferably up to 50, and more preferably 10, even more preferably 15, and most preferably 20, each in weight percent based on the total weight of monomers M1 + M2 + M3.

[0106] Such degraded starch can be obtained by known means, such as chemical degradation, catalytic degradation with a suitable catalyst or using enzymes. Preferably herein, (S) is derived from enzymatic degradation because this is a clean and fast method and there are substantially no chemical residues from the degradation reaction (except for starch and sugars from starch) in the degradation product.

[0107] The use of maltodextrin additionally provides increased stability to the dispersions of the invention at lower storage temperatures.

[0108] The aqueous polymer dispersions of the invention can be obtained with a D[4,3] value of at least 400 nm and up to 1000 nm as measured by static light scattering. Thus, such dispersions are suitable as emulsifiers in liquid formulations. The use as such an emulsifier is also claimed herein.

[0109] The aqueous polymer dispersions of the invention of any of the embodiments disclosed herein have at least one of the following properties a) to d), preferably at least two, more preferably at least three, and most preferably all of the properties defined hereinafter:

[0110] a) A transmittance of at least 20% of light at a wavelength of 532 nm when measured as a 0.01 wt% dispersion in water,

[0111] b) a pH between 2.5 and 9, preferably 3, more preferably 3.3, and even more preferably up to 7, even more preferably up to 6, even more preferably up to 5, and most preferably about 3.5;

[0112] c) a density of 1.04 to 1.08 g / mL measured as a 10 wt.% dispersion (based on solids content), and

[0113] d) a viscosity of 30 to 1000 mPas (Brookfield viscosity, spindle 3; measured on a 30 wt.% dispersion containing 30 wt.% active substance (active substance = polymer plus CGCC plus S); based on solids content; measured where concentration is applicable).

[0114] A further part of the invention is a method for producing an aqueous polymer dispersion of the invention according to any of the embodiments disclosed herein on a large scale, said method comprising

[0115] (A) polymerizing ethylenically unsaturated monomers M, where M comprises

[0116] (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

[0117] (M2) at least one (meth)acrylate optionally containing methacrylic acid as a minor component, wherein the (meth)acrylic acid in the methacrylate is bonded via an ether functional group to a polyalkylene oxide-derived block (PAO), where the PAO consists of 2 to 40 alkylene oxide (AO) units, most preferably 25 AO units, where the PAO is preferably further linked via an 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 C18 - aliphatic alkanol, where the AO is preferably selected from EO, PO, and / or BuO, more preferably at least EO, in an amount of 50, more preferably at least 75, even more preferably at least 90 wt.%, most preferably essentially only EO, based on the total AO; preferably comprising methacrylic acid, more preferably where the ratio of the methacrylate and the free methacrylic acid is about 70 w% / 30 w% to 80 w% / 20 w%, or preferably about 75 w% / 25 w%; and

[0118] (M3) optionally additional monomers copolymerizable with M1 and M2, preferably none;

[0119] The polymerization is carried out in the presence of

[0120] - at least one emulsifier,

[0121] - water,

[0122] -(CGCC) A carboxyl-containing compound in an amount of 1 to 15, preferably 2 to 10, more preferably 3 to 8, and most preferably 4 to 6% by weight based on the total weight of monomer M. The compound is selected from compounds having at least three, more preferably at least 6, 8, 10, 15, 20, 25... carboxyl groups in their structure, where at least 10 and at most 90% are deprotonated (thus forming a salt with a counterion; these counterions are selected from Na, K, NH4, Mg, Ca), and are selected from the group including: citric acid, isocitric acid; ethylenediaminetetraacetic acid; nitrilotriacetic acid; tartaric acid; oligomeric and polyacrylic acids; oligomeric and polymethacrylic acids; trimellitic acid; oligomeric amino acids with carboxyl groups, such as polyaspartic acid; oligomeric and polyglutamic acids; oligomeric and polyacetates with carboxyl groups, such as poly(glyoxylic acid) aldehyde; carboxylated oligomeric and polysaccharides, such as oxidized starch (a mixture of amylopectin and amylose); polyglucuronate; cellulose oxidized to fibroglucuronic acid; natural polycarboxylic polysaccharides, such as xylan; pectic acid; alginic acid; carboxymethylated polysaccharides based on 1,4-glucan, 1,3-glucan, 1,6-glucan; glycuronan based on 1,4-glucan, 1,3-glucan, 1,6-glucan; polygalacturonic acid; preferably carboxylated polysaccharides, more preferably carboxylated cellulose, and even more preferably carboxymethylated cellulose (carboxymethyl cellulose, "CMC"); and

[0123] -(S) At least one (non-carboxylated) sugar and / or polysaccharide, such as glucose, starch degradation products, maltodextrin, in an amount of 2 to 50, preferably 5 to 35, more preferably 10 to 30, and most preferably 15 to 25 wt% based on the total weight of monomer M,

[0124] Using at least one radical initiator or radical initiator pair, such a pair preferably comprising a peroxide and a reducing compound;

[0125] This polymerization is carried out under the following conditions

[0126] - In a reaction vessel equipped with a pressurizing device and / or a device for controlling the components during boiling, and such measures can hold the components in the reaction vessel during the reaction at an elevated temperature;

[0127] - At a temperature of 60 °C to 90 °C, preferably 70 °C to 80 °C;

[0128] - At a pH of up to 4, more preferably below 4, even more preferably at most 3.8, and even more preferably at most 3.6;

[0129] And

[0130] B) Optionally adding an additional radical initiator or initiator pair to further reduce the content of unreacted monomer and / or reduce the color of the polymer dispersion to be obtained;

[0131] C) Optionally, at least one additional reducing compound is added to reduce the color of the polymer dispersion to be obtained.

[0132] D) Optionally, at least one additional additive that may be required or desired as an additional component within the polymer dispersion to be obtained is added;

[0133] E) Optionally, the step of removing the evaporable compounds from the reaction mixture is carried out by means of a distillation step and / or a stripping step using steam or a gas, preferably steam;

[0134] F) Optionally, the step of filtering the polymer dispersion from the previous step is carried out, preferably using a 125 - micron filter;

[0135] to obtain the aqueous polymer dispersion.

[0136] As a result of the polymerization reaction, the aqueous dispersion may contain sulfite and / or sulfate ions. These are mainly generated by the use of a persulfate radical initiator.

[0137] During the polymerization process, due to the formation of acid by the use of a persulfate initiator, the pH value of the mixture typically decreases. In principle, this decrease in pH can be minimized by adding a base. However, the use of a base is not preferred. As the amount of electrolyte increases, the more base is added, the amount of coagulum typically increases.

[0138] In a preferred embodiment P1 of the method as defined above, for the main polymerization step, at least one persulfate is used as a radical polymerization initiator together with ascorbic acid and / or iso - ascorbic acid.

[0139] In a preferred embodiment P2 of the method as defined above, and preferably in combination with any of the previous embodiments, the radical polymerization initiator additionally contains 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, etc. Such complexes in combination with a persulfate radical initiator for such applications are known.

[0140] In a preferred embodiment P3 of the method as defined above, and preferably in combination with any of the previous embodiments, in the post - polymerization step, at least one hydroperoxide and at least one sulfite are used.

[0141] In a preferred embodiment P3 of the method as defined above, and preferably in combination with any of the previous embodiments, at least 5% of the total amount of the hydroperoxide added in the post - polymerization step is added after the addition of the sulfite is completed.

[0142] In a preferred embodiment P4 of the method as defined previously, and preferably in combination with any of the previous embodiments, volatile components are removed using steam distillation, thermal distillation, vacuum distillation, gas stripping to reduce and preferably substantially remove to a level required or acceptable for the intended application area the remaining amount of one or more monomers M1 and reaction by-products. This step is carried out at ambient pressure, reduced pressure or overpressure up to 2 bar absolute pressure to reduce the content of one or more organic solvents and residual volatile monomers such as vinyl esters to at most 1 wt%, preferably at most 0.5, more preferably at most 0.01% by weight based on the total weight of the obtained polymer dispersion.

[0143] In a preferred embodiment P5 of the method as defined previously, and preferably in combination with any of the previous embodiments, the dispersion finally obtained after the last method step of polymerization and – if used – purification is filtered to remove polymer agglomerates with a size exceeding 125 microns.

[0144] Use

[0145] A further part of the invention is the use of an aqueous polymer dispersion as detailed previously herein, and / or an aqueous polymer dispersion obtainable by the method as detailed previously herein as an emulsifier in liquid formulations and liquid compositions. More precisely, such an aqueous polymer dispersion is preferably used in the field of cleaning compositions for use on fabrics and / or hard surfaces and for industrial and institutional cleaning.

[0146] Another part of the invention is a liquid or semi-liquid formulation or composition comprising at least one aqueous polymer dispersion as detailed previously herein, and / or an aqueous polymer dispersion obtainable by the method as detailed previously herein, for use in the field of cleaning compositions for use on fabrics and / or hard surfaces and for industrial and institutional cleaning. Preferably, such an aqueous polymer dispersion is used therein as an emulsifier.

[0147] Another part of the invention is a liquid or semi-liquid detergent composition comprising at least one aqueous polymer dispersion as detailed previously herein, and / or an aqueous polymer dispersion obtainable by the method as detailed previously herein. Such a composition is preferably a laundry detergent, a manual dishwashing detergent, an automatic dishwashing detergent, or a hard surface cleaner, more preferably for use in the fields of household and fabric care.

[0148] Preferably, such an aqueous polymer dispersion is used therein as an emulsifier.

[0149] Accordingly, a preferred subject matter of the present invention is still at least one aqueous polymer dispersion as detailed hereinbefore, and / or the use of an aqueous polymer dispersion obtainable by a method as detailed hereinbefore in fabric care and household care products, preferably in cleaning compositions, and in fabric treatment agents, fabric care products and fabric washing products, more preferably in fabric detergent formulations, even more preferably in liquid fabric detergent formulations. In particular, the aqueous polymer dispersion is used in such compositions / products / formulations to impart opacity.

[0150] Such uses of the present invention cover the use of at least one aqueous polymer dispersion as detailed hereinbefore, and / or an aqueous polymer dispersion obtainable by a method as detailed hereinbefore, such polymer dispersion being similar to the polymer dispersion detailed above, and describing the polymer structure in all of its embodiments, variants, and preferred, more preferred, etc. embodiments.

[0151] Accordingly, another subject matter of the present invention is a cleaning composition, fabric care and household care product, preferably a fabric cleaning composition, fabric treatment product or fabric care product or fabric washing product, more preferably a liquid fabric detergent formulation or a liquid fabric detergent product, which contains at least one aqueous polymer dispersion as detailed hereinbefore, and / or an aqueous polymer dispersion obtainable by a method as detailed hereinbefore, such composition or product exhibiting improved opacity.

[0152] Such compositions or products of the present invention cover the use of at least one aqueous polymer dispersion as detailed hereinbefore, and / or an aqueous polymer dispersion obtainable by a method as detailed hereinbefore, such polymer dispersion being similar to the polymer dispersion detailed above, and describing the polymer structure in all of its embodiments, variants, and preferred, more preferred, etc. embodiments.

[0153] In one embodiment, it is further preferred that the cleaning composition, fabric care and household care product, preferably a fabric cleaning composition, fabric treatment product or fabric care product or fabric washing product, more preferably a liquid fabric detergent formulation or a liquid fabric detergent product contains at least one aqueous polymer dispersion as detailed hereinbefore, and / or an aqueous polymer dispersion obtainable by a method as detailed hereinbefore, such composition or product preferably exhibiting improved opacity and additionally containing at least one enzyme, which enzyme is preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, mannanases, xylanases, deoxyribonucleases, dispersin, pectinases, oxidoreductases, hemicellulases, phospholipases, esterases, pectinases, cutinases, lactases and peroxidases, and combinations of at least two of the foregoing types, preferably at least one protease.

[0154] At least one aqueous polymer dispersion as detailed hereinbefore, and / or an aqueous polymer dispersion obtainable by a method as detailed hereinbefore, is present in the compositions and products of the present invention in an amount of from about 0.01% to about 10%, preferably from 0.02% to 5%, more preferably from about 0.05% to 3%, even more preferably from about 0.1% to about 2% and further more preferably from about 0.15% to about 2% and most preferably up to 1.5%, such as up to 1%, by weight, each based on the weight % of the total weight of such composition or product, and further includes all ranges resulting from choosing any lower limit and any upper limit and all numbers between the mentioned lower and upper limits; such compositions or products may - and preferably do - further comprise a surfactant system in an amount of from about 1% to about 70% by weight of the composition or product; the compositions and products are intended to be used as fabric care compositions.

[0155] Even more preferably, the compositions or products of the present invention as detailed above, which comprise at least one aqueous polymer dispersion as detailed hereinbefore, and / or an aqueous polymer dispersion obtainable by a method as detailed hereinbefore, and optionally further comprise at least one surfactant or surfactant system in an amount of from about 1% to about 70% by weight of the composition or product, are those for primary cleaning (i.e., stain removal) in laundry applications and may additionally comprise at least one enzyme, which is preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, mannanases, xylanases, deoxyribonucleases, dispersing enzymes, pectinases, oxidoreductases, hemicellulases, phospholipases, esterases, pectinases, cutinases, lactases and peroxidases, and combinations of at least two of the foregoing types, preferably at least one protease.

[0156] In a preferred embodiment, the cleaning composition of the present invention is a liquid or semi-liquid laundry detergent composition, preferably a liquid laundry detergent composition.

[0157] In one embodiment, the aqueous polymer dispersion of the present invention can be used in a cleaning composition or product comprising a surfactant system comprising C10-C15 alkylbenzene sulfonate (LAS) as the main surfactant and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

[0158] In a further embodiment, the aqueous polymer dispersion of the present invention can be used in cleaning compositions or fabric and home care products, preferably in laundry cleaning compositions, laundry care products or laundry treatment products or laundry washing products, preferably in liquid laundry detergent formulations or liquid laundry detergent products, which comprise a C8-C18 linear or branched alkyl ether sulfate having 1-5 ethoxy units as the main surfactant and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

[0159] In one embodiment of the present invention, the aqueous polymer dispersion is a component of a cleaning composition or fabric and home care product which additionally comprises at least one surfactant, preferably at least one anionic surfactant, preferably a component of a laundry cleaning composition, a laundry care product or a laundry treatment product or a laundry washing product, preferably a component of a liquid laundry detergent formulation or a liquid laundry detergent product.

[0160] In a further embodiment, the present invention also encompasses a composition which comprises the aqueous polymer dispersion as described above and further comprises an antimicrobial agent (preferably selected from the group consisting of 2-phenoxyethanol) as disclosed below, more preferably comprises the antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition; even more preferably comprises 0.1% to 2% of phenoxyethanol.

[0161] In a further embodiment, the present invention also encompasses a method of preserving an aqueous composition against microbial contamination or growth, such composition comprising the aqueous polymer dispersion as described above, such composition preferably being a detergent composition, such method comprising adding at least one antimicrobial agent selected from the antimicrobial agents disclosed below, such antimicrobial agent preferably being 2-phenoxyethanol.

[0162] 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 dish composition, even more preferably a liquid laundry detergent composition or a liquid fabric softener composition for laundry, such composition comprising the aqueous polymer dispersion as described above, such composition further comprising 4,4'-dichloro-2-hydroxy diphenyl 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.

[0163] In further embodiments, the present invention also encompasses a method of laundering fabrics or cleaning hard surfaces, the method comprising treating the fabric or hard surface with a cleaning composition, more preferably a liquid laundry detergent composition or a liquid manual dish composition, even more preferably a liquid laundry detergent composition or a liquid fabric softener composition for laundry, such composition comprising an aqueous polymer dispersion as described above, such composition further comprising 4,4'-dichlor-2-hydroxy diphenyl ether.

[0164] In these embodiments, the selection of these additional surfactants and additional cleaning aids can depend on the application and the desired benefits.

[0165] Preferably, the cleaning compositions of the present invention are those for the fields of laundry detergent compositions and detergents for laundry and manual dishwashing compositions. More preferably, the cleaning compositions of the present invention are liquid compositions for use in the fields of laundry and hard surface cleaning, such as liquid laundry detergents and liquid dishwashing cleaning compositions, preferably for manual dishwashing and for laundry.

[0166] The cleaning composition can have a form selected from the following: liquid, powder, single-phase or multi-phase unit dose, pouch, tablet, gel, paste, bar or sheet. The preferred cleaning composition is liquid or semi-liquid. More preferably, the cleaning composition is liquid.

[0167] Compositions and formulations for industrial and institutional cleaning include those designed to clean any kind of soiled material or surface, such as hard surface cleaners for any kind of surface (including tiles, carpets, PVC-surfaces, wooden surfaces, metal surfaces, painted surfaces).

[0168] The cleaning composition comprises 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 a surfactant system, by weight of the composition.

[0169] In other embodiments, the liquid cleaning composition comprises from about 2% to about 60% of a surfactant system, by weight of the composition. In further embodiments, the cleaning composition comprises from about 5% to about 30% of a surfactant system, by weight of the composition. The surfactant system can comprise detergency surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, and mixtures thereof. One of ordinary skill in the art will understand that detergency surfactants encompass any surfactant or mixture of surfactants that provides cleaning, stain removal, or washing benefits to soiled materials.

[0170] The cleaning composition may also contain auxiliary cleaning additives. Suitable auxiliary cleaning additives include builders, structuring or thickening agents, clay soil removal / antiredeposition agents, polymeric soil release agents, polymeric dispersants, polymeric grease cleaners, enzymes, enzyme stabilizing systems, bleaching compounds, bleaches, bleach activators, bleach catalysts, brighteners, dyes, colorants, dye transfer inhibitors, chelating agents, foam inhibitors, softeners, and fragrances.

[0171] All such cleaning compositions, their ingredients, their general compositions, and more specific compositions are known, as shown, for example, in publications 800542 and 800500 published by Protegas, Liechtenstein, and also in WO 2022 / 136409 and WO 2022 / 136408, where the emulsion compounds – if actually used therein or only considered for use – can be partially or completely replaced by the aqueous polymer dispersions of the present invention; if not used, the aqueous polymer dispersions of the present invention can be added in the amounts given in the present invention. In those aforementioned documents, various types of formulations for cleaning compositions are also disclosed; all such composition types can equally well be applicable to those cleaning compositions contemplated herein.

[0172] In each of the foregoing application areas and their compositions and formulations, the aqueous polymer dispersions of the present invention are preferably used as opacifiers to impart opacity to such formulations and compositions, such as, for example, to impart turbidity to an otherwise transparent liquid formulation or a formulation containing undissolved or emulsified components, and thereby to "hide" those undissolved or emulsified portions of the composition or formulation by imparting turbidity, and thereby making such portions less visible, or – in the case of a transparent (and preferably also colorless or only faintly colored) formulation or composition, to increase visibility by imparting turbidity. Turbidity can also be used to alter the visual observation of color by imparting turbidity and thus by increasing the amount of scattered light and thus, for example, enhancing color, reducing gloss, or otherwise to create a different perception of that color.

[0173] As used herein, the phrase " Cleaning composition " includes compositions and formulations designed for cleaning soiled materials. Such compositions and formulations include those designed for cleaning any kind of soiled material or surface, and specifically include compositions for fabric and home care.

[0174] Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry pre-washes, laundry pre-treatments, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, wash additives, post-rinse fabric treatments, ironing aids, dishwashing compositions, hard surface cleaning compositions, single-dose formulations, delayed delivery formulations, detergents incorporated on or in a porous substrate or nonwoven sheet, 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 as pre-wash treatments, post-wash treatments, or can be added during the rinse or wash cycles of a washing operation.

[0175] Compositions for " Industrial and institutional cleaning " include such cleaning compositions designed for industrial and institutional cleaning, such as those for cleaning any kind of soiled material or surface, such as hard surface cleaners for any kind of surface (including tile, carpet, PVC surfaces, wooden surfaces, metal surfaces, painted surfaces).

[0176] The phrase "fabric care composition" means compositions and formulations designed for treating fabrics. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry pre-washes, laundry pre-treatments, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, wash additives, post-rinse fabric treatments, ironing aids, single-dose formulations, delayed delivery formulations, detergents incorporated on or in a porous substrate or nonwoven sheet, and other suitable forms that will be apparent to those skilled in the art in view of the teachings herein and are further detailed below when describing the uses and applications of the compositions. Such compositions can be used as pre-wash treatments, post-wash treatments, or can be added during the rinse or wash cycles of a washing operation and are further detailed below when describing the uses and applications of the aqueous polymer dispersions and compositions containing such dispersions of the present invention.

[0177] "Compositions for fabric and home care" include cleaning compositions, including but not limited to laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric brightening compositions, laundry pre-wash compositions, laundry pre-treatment agents, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, wash additives, post-rinse fabric treatment agents, 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 for laundry, bleaching compositions, laundry additives, fabric enhancer compositions, and other suitable forms that would be apparent to those skilled in the art in view of the teachings herein. Such compositions can be used as pre-wash treatments, post-wash treatments, or can be added during the rinse or wash cycles of a washing operation, preferably during the wash cycle of a laundry or dishwashing operation. More preferably, such compositions for fabric and home care are laundry cleaning compositions, laundry care products, or laundry washing products, and most preferably liquid laundry detergent formulations or liquid laundry detergent products.

[0178] The cleaning compositions of the present invention can be in any form, namely in the form of "liquid" compositions, including composition types containing liquids such as pastes, gels, emulsions, foams, and mousses; in the form of solid compositions, such as powders, granules, microcapsules, beads, noodles, pearlescent balls, agglomerates, tablets, granule compositions, sheets, lozenges, beads, fibrous products, strips, flakes; or mixtures thereof, of the type delivered in single-, double-, or multi-compartment bags or containers; single-phase or multi-phase unit doses; spray or foam detergents; pre-moistened wipes (i.e., cleaning compositions combined with nonwoven materials, such as the cleaning compositions discussed in US 6,121,165, Mackey et al.); dry wipes (i.e., cleaning compositions combined with nonwoven materials, such as the cleaning compositions discussed in US 5,980,931, Fowler et al.), which are activated by the user or consumer with water; and other homogeneous, heterogeneous, single-phase or multi-phase cleaning product forms.

[0179] The composition can be encapsulated in a single or multi-compartment bag. The multi-compartment bag can have at least two, at least three, or at least four compartments. The multi-compartment bag can include side-by-side and / or stacked compartments. The composition contained in the bag or its compartments can be liquid, solid (such as powder), or a combination thereof.

[0180] Non-limiting examples of "liquid" / "liquid composition" include light-duty and heavy-duty liquid detergent compositions, fabric enhancers, detergent gels commonly used for laundry, bleaching and laundry additives. Gases, such as suspended air bubbles, or solids, such as particles, may be contained in the liquid.

[0181] The liquid cleaning composition of the present invention preferably has a viscosity of 50 to 10,000 mPa·s; at 20 1 / s and 20 °C, the liquid dishwashing composition for handwashing (also known as the liquid manual "dishwashing composition") preferably has 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 1 / s and 20 °C, the liquid laundry cleaning composition preferably has 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.

[0182] The liquid cleaning composition of the present invention can have any suitable pH value. Preferably, the pH of the composition is adjusted to between 4 and 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-modifying ingredients known in the art and is measured at 25 °C in demineralized water at a 10% product concentration. For example, NaOH can be used and the actual weight% of NaOH can be varied and trimmed to the desired pH such as pH 8.0. In one embodiment of the present invention, the pH > 7 is adjusted by using amines, preferably alkanolamines, more preferably triethanolamine.

[0183] Cleaning compositions, such as fabric and home care products and formulations for industrial and institutional cleaning, more specifically such as laundry detergents and detergents for manual dishwashing, are known to those skilled in the art. Any composition known to those skilled in the art, etc. (in combination with their respective uses), can be used within 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 exhibiting certain properties within such a composition (especially when such a composition is used in its field of use).

[0184] One aspect of the present invention is also the use of the polymer of the present invention as an additive for detergent formulations, especially for liquid detergent formulations, preferably concentrated liquid detergent formulations, or single-dose single-use additives for laundry.

[0185] The cleaning composition of the present invention can - and preferably does - contain auxiliary cleaning additives (also abbreviated as "auxiliaries" herein), and such auxiliaries are preferably in addition to the surfactant system as defined previously.

[0186] Suitable auxiliary cleaning additives include builders, cobuilders, surfactant systems, fatty acids and / or their salts, structurants, thickeners and rheology modifiers, clay / dirt removal / antiredeposition agents, polymeric soil release agents, dispersants such as polymeric dispersants, polymeric grease cleaners, solubilizers, amphiphilic copolymers (including those without vinylpyrrolidone), chelating agents, enzymes, enzyme stabilization systems, encapsulated benefit agents such as encapsulated fragrances, bleaching compounds, bleaches, bleach activators, bleach catalysts, catalytic materials, brighteners, malodor control agents, pigments, dyes, opacifiers, pearlescents, colorants, dye transfer inhibitors, fabric softeners, carriers, foam boosters, foam inhibitors (defoamers), color speckle removers, silver care agents, anti-discoloration agents and / or anti-corrosion agents, sources of alkalinity, pH regulators, pH buffers, hydrotropes, washing granules, antibacterial and antimicrobial agents, preservatives, antioxidants, softeners, carriers, fillers, solvents, processing aids, pro-perfumes and fragrances.

[0187] Suitable examples and levels of use of such cleaning aids can be seen, for example, in WO 99 / 05242, U.S. Patent Nos. 5,576,282, 6,306,812B1 and 6,326,348B1.

[0188] All such cleaning compositions, their ingredients (including (auxiliary) cleaning additives), their general compositions and more specific compositions are in principle known, as shown, for example, in the publications 800542 and 800500 published by Protegas AG of Liechtenstein, as well as in WO 2022 / 136409 and WO 2022 / 136408, where in any of those prior art documents, the general compositions disclosed in those prior publications and also the opacifiers in each individualized specific cleaning composition can be partially or completely replaced by the dispersions of the present invention. In those prior documents, various types of formulations for cleaning compositions are also disclosed; all such composition types - general compositions as well as each individualized specific cleaning composition - can equally apply to those cleaning compositions contemplated herein.

[0189] Accordingly, the present invention also encompasses any and all such disclosed compositions of the aforementioned prior art disclosures, but in addition to or in place of any emulsifiers of such prior art compositions already included, further comprising at least one of the dispersions of the present invention, which emulsifiers may be replaced by such dispersions of the present invention - such replacement is known in principle to the person skilled in the art -, wherein the content of the dispersions of the present invention is present in the formulation at a concentration of generally from 0.05 to 20 wt.%, preferably up to 10 wt.%, more preferably from 0.1 to 5 wt.%, even more preferably from 0.5 to 2 wt.%, and most preferably up to 1 wt.%.

[0190] In addition to the surfactant system and the graft polymer, the liquid cleaning composition may additionally comprise - and preferably does comprise - at least one of the following: a rheology control agent / modifier, an emollient, a wetting agent, a skin rejuvenating active, and a solvent.

[0191] The solid composition may additionally comprise - and preferably does comprise - at least one of a filler, a bleach, a bleach activator, and a catalytic material.

[0192] One of ordinary skill in the art will understand that a detersive surfactant encompasses any surfactant or mixture of surfactants that provides cleaning, stain removal, or washing benefits to soiled materials.

[0193] Accordingly, the cleaning compositions of the present invention, such as fabric and home care products, as well as formulations for industrial and institutional cleaning, more particularly such as laundry detergents and dishwashing detergents for manual dishwashing, preferably additionally comprise a surfactant system, and more preferably also comprise additional adjuvants.

[0194] The surfactant system may consist of one surfactant or a combination of surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. One of ordinary skill in the art will understand that a surfactant system for detergents encompasses any surfactant or mixture of surfactants that provides cleaning, stain removal, or washing benefits to soiled materials.

[0195] The cleaning composition of the present invention preferably comprises 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 mixtures thereof.

[0196] The cleaning composition of the present invention may - in addition to all other ingredients mentioned - further comprise one or more enzymes selected from those disclosed above, more preferably protease and / or amylase, wherein even more preferably the protease is a protease having at least 90% sequence identity with SEQ ID NO:22 of EP1921147B1 and having the amino acid substitution R101E (numbering according to BPN), and wherein the amylase is an amylase having at least 90% sequence identity with SEQ ID NO:54 of WO 2021032881A1, and said one or more enzymes are preferably present in the formulation at a level of from about 0.00001% to about 5%, preferably from about 0.00001% to about 2%, more preferably from about 0.0001% to about 1%, or even more preferably from about 0.001% to about 0.5% enzyme protein by weight of the composition.

[0197] The following compositions shown below (including those in the tables) disclose certain types of general cleaning compositions corresponding to typical compositions related to typical washing conditions typically employed in various regions and countries of the world. The at least one dispersion of the present invention can be added to such formulations in a suitable amount as outlined herein. When the compositions shown do not contain the dispersion of the present invention, such compositions are comparative compositions. When they contain the dispersion of the present invention, especially in amounts within the ranges described as preferred, more preferred, etc. herein, such compositions are considered to fall within the scope of the present invention.

[0198] (Hereinafter, all weight percentages; if the ingredient is added as a solution or dispersion, the percentage relates to the active substance content, i.e., generally the solid content of the ingredient in such solution or dispersion)

[0199] The liquid laundry detergent according to the present invention consists of:

[0200] 0.05% - 5% of at least one aqueous polymer dispersion (% by solid content)

[0201] At least one cleaning polymer of 0.05%-10%

[0202] 1%-50% surfactant

[0203] 0.1%-40% builder, cobuilder and / or chelating agent

[0204] 0.1%-50% other adjuvants

[0205] Water, making up 100% in total.

[0206] The preferred liquid laundry detergent according to the invention consists of:

[0207] 0.15%-3% of at least one aqueous polymer dispersion (% by solid content)

[0208] 0.2%-10% of at least one cleaning polymer

[0209] 5%-40% of anionic surfactant selected from C10-C15-LAS and C10-C18 alkyl ether sulfates containing 1-5 ethoxy units

[0210] 1.5%-10% of nonionic surfactant selected from C10-C18-alkyl ethoxylates containing 3-10 ethoxy units

[0211] 2%-20% of soluble organic builders / cobuilders selected from C10-C18 fatty acids, di- and tricarboxylic acids, hydroxy-dicarboxylic acids and hydroxytricarboxylic acids, aminopolycarboxylates and polycarboxylic acids

[0212] 0.05%-5% of an enzyme system containing at least one enzyme suitable for detergent use and preferably also an enzyme stabilization system

[0213] 0.5%-20% of monoalcohol or diol selected from ethanol, isopropanol, ethylene glycol, or propylene glycol

[0214] 0.1%-20% other adjuvants

[0215] Water, making up 100% in total.

[0216] In a preferred embodiment, at least one compound according to the invention is used in a detergent for manual dishwashing.

[0217] The liquid detergent for manual dishwashing according to the invention consists of:

[0218] 0.05%-5% of at least one dispersion of the invention

[0219] 1%-50% surfactant

[0220] 0.1%-50% of other adjuvants

[0221] Water, totaling 100%.

[0222] The preferred liquid manual dishwashing detergent according to the present invention consists of the following:

[0223]

[0224] General formulation of the laundry detergent composition according to the present invention:

[0225] Ingredients Range of ingredients in liquid frame formulations Linear alkylbenzene sulfonic acid 0% to 30% Coconut fatty acid 1% to 12% Fatty alcohol ether sulfate 0% to 25% NaOH or mono- or triethanolamine Up to pH 7.5 to 9.0 Alcohol ethoxylate 3% to 10% 1,2 - Propylene glycol 1% to 10% Ethanol 0% to 4% Sodium citrate 0% to 8% Water Make up to 100%

[0226] Liquid laundry frame formulation according to the present invention:

[0227]

[0228]

[0229] The following three tables show additional typical liquid detergent formulations LD1, LD2, and LD3: Liquid Detergent 1 - LD1

[0230] Liquid detergent formulation <![CDATA[Sodium linear alkyl benzene sulfonate (C 10 -C 13 ) LAS]]> 9.5％ <![CDATA[C reacted with 7 moles of EO 13 / C 15 -oxoalkanol]]> 4,5％ 1,2 - Propylene glycol 6％ Ethanol 2％ Potassium coconut soap 2.4％ NaOH 2.2％ Lauryl ether sulfate (Texapon) 5.0％ Sodium citrate 3％ Sokalan HP 20 2％ Graft polymer* 2％ Other polymers 1％-4％ Aqueous polymer dispersion 0.5％ Water Make up to 100%

[0231] Liquid Detergent 2 - LD2

[0232] Liquid detergent formulation <![CDATA[Sodium alkylbenzenesulfonate (C 10 -C 13 )]]> 5.5％ <![CDATA[C reacted with 7 moles of EO 13 / C 15 -oxoalkanol]]> 5.4％ 1,2 - Propylene glycol 6％ Ethanol 2％ Potassium coconut soap 2.4％ Monoethanolamine 2.5％ Lauryl ether sulfate 5.4％ Sodium citrate 3％ Sokalan HP96 2％ Graft polymer* 2％ Other polymers 3％ Aqueous polymer dispersion 0.1％ Water Make up to 100%

[0233] Liquid Detergent 3 - LD3

[0234] Liquid detergent formulation MGDA 5.5％ APG, branched C13 glucoside 3.5％ 1,2 - Propylene glycol 6％ Ethanol 2％ Potassium coconut soap 4.4％ NaOH 2.2％ Lauryl ether sulfate 9.5％ Sodium citrate 3％ Graft polymer* 2％ Other polymers 1％-4％ Aqueous polymer dispersion 1％ Water Make up to 100%

[0235] All of the previous three tables: * Polyethylene glycol with Mn 6000 g / mol as the grafting matrix, grafted with 60% by weight of vinyl acetate (based on the total polymer weight; produced according to the general disclosure of WO 2007138054A1)

[0236] Liquid manual dishwashing frame formulation according to the present invention:

[0237]

[0238] Preferably, in the corresponding laundry detergent, cleaning composition and / or fabric and home care product, at least one aqueous polymer dispersion is present in a concentration of from about 0.01% to about 10%, preferably from 0.02% to 5%, more preferably from about 0.05% to 3%, even more preferably from about 0.1% to about 2%, and still more preferably from about 0.15% to about 2%, and most preferably in an amount up to 1.5%, such as up to 1%, each based on the weight % of the total weight of such composition or product, and further including all ranges resulting from selecting any lower limit and any upper limit and all numbers between the mentioned lower and upper limits

[0239] This invention encompasses the specific embodiments described throughout this disclosure as part of the invention; the various additional options disclosed in this specification as "optional", "preferred", "more preferred", "even more preferred" or "most preferred" options of the specific embodiments can be selected individually and independently (unless such independent selection is not possible due to the nature of the feature or if such independent selection is explicitly excluded), and then combined within any other embodiment (where other such options and preferences can also be selected individually and independently), where each and any and all such possible combinations are included as separate embodiments as part of the invention.

[0240] Most preferred embodiment

[0241] Example 1

[0242] An aqueous polymer dispersion obtainable by free radical aqueous emulsion polymerization of a mixture comprising

[0243] a) ethylenically unsaturated monomer M, wherein M comprises

[0244] (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

[0245] (2) (M2) At least one (meth)acrylate optionally containing methacrylic acid as a minor component, wherein the (meth)acrylic acid in the methacrylate is bonded to a polyalkylene oxide-derived block (PAO) via an ether functional group, where the PAO consists of 2 to 40 alkylene oxides (AO), most preferably 25 AO units, and where the PAO is preferably further linked via an 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 C18 - aliphatic alkanol, and where the AO is preferably selected from EO, PO, and / or BuO, more preferably at least EO, with an amount of 50, more preferably at least 75, even more preferably at least 90 wt.% based on the total AO, most preferably essentially only EO; preferably contains methacrylic acid, and more preferably the ratio of the methacrylate to the free methacrylic acid is about 70 w% / 30 w% to 80 w% / 20 w%, more preferably about 75 w% / 25 w%;

[0246] (3) (M3) Optionally additional monomers polymerizable with M1 and M2, preferably none;

[0247] b) (CGCC) Based on the total weight of monomer M, 1 to 15, preferably 2 to 10, more preferably 3 to 8, most preferably 4 to 6% by weight of a carboxyl-containing compound, which compound is selected from compounds having at least three, more preferably at least 6, 8, 10, 15, 20, 25... carboxyl groups in its structure, where at least 10 and at most 90 percent are deprotonated (thus forming a salt with a counterion; these counterions are selected from Na, K, NH4, Mg, Ca,...), and are selected from the group including: citric acid, isocitric acid; ethylenediaminetetraacetic acid; nitrilotriacetic acid; tartaric acid; oligomeric and polyacrylic acids; oligomeric and polymethacrylic acids; trimellitic acid; oligomeric amino acids with carboxyl groups, such as polyaspartic acid; oligomeric and polyglutamic acids; oligomeric and polyacetates with carboxyl groups, such as poly(glyoxylic acid) aldehyde; carboxylated oligomeric and polysaccharides, such as oxidized starch (a mixture of amylopectin, amylose); polyglucuronate; cellulose oxidized to glucuronic acid; natural polycarboxylic polysaccharides, such as xylan; pectic acid; alginic acid; carboxymethylated polysaccharides based on 1,4 - glucan, 1,3 - glucan, 1,6 - glucan; glycuronan based on 1,4 - glucan, 1,3 - glucan, 1,6 - glucan; polygalacturonic acid; preferably carboxylated polysaccharides, more preferably carboxylated cellulose, even more preferably carboxymethylated cellulose (carboxymethyl cellulose, "CMC"); and

[0248] c) (S) At least one (non - carboxylated) sugar and / or polysaccharide, such as glucose, starch degradation products, maltodextrin, with an amount of 2 to 50, preferably 5 to 35, more preferably 10 to 30, most preferably 15 to 25 wt% based on the total weight of monomer M,

[0249] and

[0250] d) at least one emulsifier selected from non-ionic and anionic surfactants, wherein

[0251] i) the at least one ionic surfactant is selected from:

[0252] anionic emulsifiers bearing at least one anionic group selected from phosphate, phosphonate, sulfate and sulfonate groups;

[0253] the anionic emulsifier is typically used in the form of its alkali metal salts (especially its sodium salts) or in the form of its ammonium salts;

[0254] preferably, the anionic emulsifier bears at least one sulfate or sulfonate group or at least one phosphate or phosphonate group, more preferably bears at least one sulfonate or sulfate group, most preferably only one sulfonate or one sulfate group,

[0255] a) wherein the anionic emulsifier bearing at least one sulfate or sulfonate group is preferably selected from

[0256] - salts of alkyl sulfates, especially salts of C8-C22-alkyl sulfates, especially alkali metal salts and ammonium salts,

[0257] - monoesters of sulfuric acid of C2-C3-alkoxylated alkanols, especially salts of monoesters of sulfuric acid of C2-C3-alkoxylated C8-C22-alkanols (preferably having a C2-C3-alkoxylation level (AO level) in the range from 2 to 40), especially alkali metal salts and ammonium salts,

[0258] - monoesters of sulfuric acid of C2-C3-alkoxylated alkylphenols, especially salts of monoesters of sulfuric acid of C2-C3-alkoxylated C4-C18-alkylphenols (AO level preferably 3 to 40), especially alkali metal salts and ammonium salts,

[0259] - alkyl sulfonic acids, especially salts of C8-C22-alkyl sulfonic acids, especially alkali metal salts and ammonium salts,

[0260] - dialkyl esters of sulfosuccinic acid, especially salts of di-C4-C18-alkyl esters, especially alkali metal salts and ammonium salts,

[0261] - alkylbenzenesulfonic acids, especially salts of C4-C22-alkylbenzenesulfonic acids, especially alkali metal salts and ammonium salts, and

[0262] - mono- or disulfonated alkyl-substituted diphenyl ethers, such as salts of bis(benzenesulfonic acid) ethers bearing C4-C24-alkyl on one or both aromatic rings, especially alkali metal salts and ammonium salts;

[0263] The term "C2-C3-alkoxylation" means that these compounds are ethoxylated, propoxylated or co-ethoxylated / propoxylated, i.e. it means that the corresponding compounds are obtained by introducing poly(ethylene oxide) groups, poly(propylene oxide) groups or poly(ethylene oxide - co - propylene oxide) groups;

[0264] b) wherein the anionic emulsifier bearing at least one phosphate or phosphonate group is preferably selected from

[0265] - salts of mono - and dialkyl phosphates, especially C8 - C22 - alkyl phosphates, especially alkali metal salts and ammonium salts,

[0266] - monoesters of phosphoric acid of C2 - C3 - alkoxylated alkanols (preferably having an alkoxylation level in the range from 2 to 40, especially in the range from 3 to 30), such as monoesters of phosphoric acid of ethoxylated C8 - C22 - alkanols (preferably having an ethoxylation level (EO level) in the range from 2 to 40), monoesters of phosphoric acid of propoxylated C8 - C22 - alkanols (preferably having a propoxylation level (PO level) in the range from 2 to 40) and monoesters of phosphoric acid 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 from 1 to 20), especially alkali metal salts and ammonium salts,

[0267] - salts of monoesters of phosphoric acid of C2 - C3 - alkoxylated alkylphenols, especially monoesters of phosphoric acid of C2 - C3 - alkoxylated C4 - C18 - alkylphenols (AO level preferably 3 to 40), especially alkali metal salts and ammonium salts,

[0268] - salts of alkylphosphonic acids, especially C8 - C22 - alkylphosphonic acids, especially alkali metal salts and ammonium salts, and

[0269] - salts of alkylbenzenephosphonic acids, especially C4 - C22 - alkylbenzenephosphonic acids, especially alkali metal salts and ammonium salts;

[0270] wherein the more preferred anionic emulsifiers are selected from the group consisting of:

[0271] - salts of alkyl sulfates, especially C8 - C22 - alkyl sulfates, especially alkali metal salts and ammonium salts,

[0272] - monoesters of sulfuric acid of C2 - C3 - alkoxylated alkanols, especially salts of monoesters of sulfuric acid of C2 - C3 - alkoxylated C8 - C22 - alkanols (preferably having an AO level in the range from 2 to 40), especially alkali metal salts,

[0273] - monoesters of sulfuric acid of C2 - C3 - alkoxylated alkylphenols, especially monoesters of sulfuric acid of C2 - C3 - alkoxylated C4 - C18 - alkylphenols (AO level preferably 3 to 40),

[0274] - Alkylbenzenesulfonic acids, especially C4-C22-alkylbenzenesulfonic acids, and

[0275] - Mono- or disulfonated alkyl-substituted diphenyl ethers, such as bis(phenylsulfonic acid) ethers with C4-C24-alkyl groups on one or both aromatic rings;

[0276] ii) The at least one nonionic surfactant is selected from:

[0277] The nonionic emulsifier is, for example, an araliphatic or aliphatic nonionic emulsifier selected from the following

[0278] - C2-C3-alkoxylated mono-, di- and trialkylphenols, where the number of repeating units of the alkylene oxide-derived moiety is preferably 3 to 50, and / or the alkyl group is preferably a C4-C10-alkyl group;

[0279] - C2-C3-alkoxylates of long-chain alcohols, such as ethoxylates, propoxylates or ethoxylate-copropoxylates, where the number of repeating units of the alkylene oxide-derived moiety is preferably 3 to 100, and / or the alkyl group is preferably a C8-C36-alkyl group, and

[0280] - Polyethylene oxide / polypropylene oxide homopolymers and copolymers, which may contain alkylene oxide units copolymerized in a random distribution or in the form of block or mixtures of homopolymeric blocks and random blocks,

[0281] More preferably, the C2-C3-alkoxylation of long-chain alkanols, especially those with an average alkoxylation level of 5 to 100 for alkyl C8-C30, and among these, those with a straight-chain C12-C20 alkyl group and an average alkoxylation level of 10 to 50 are particularly preferred, and also C2-C3-alkoxylated monoalkylphenols;

[0282] And

[0283] e) Optionally sulfate ions, and

[0284] f) Optionally sulfite ions,

[0285] where – preferably the amount of M1 is 80 to 99.99 mol%, more preferably the amount of M1 is at least 98%, and the amount of M2 is 0.01 to 20 mol%, more preferably 0.1, even more preferably 0.2, even more preferably 0.5, and most preferably 0.7, and preferably at most 10, even more preferably at most 5, more preferably at most 2, and most preferably, the amount of M1 is about 99 weight percent and the amount of M2 is about 1 weight percent, the total amount of M1 plus M2 is 100 weight percent, and

[0286] wherein the dispersion has, after the polymerization is complete, a pH of up to 4, more preferably below 4, even more preferably at most 3.8, even more preferably at most 3.6, and 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.

[0287] Example 2

[0288] The dispersion according to claim 1, wherein,

[0289] (M1) the vinyl ester monomer comprises at least 50%, even more preferably at least 90%, based on the total molar amount of the vinyl ester, of vinyl acetate, and

[0290] (M2) the at least one (meth)acrylate is (meth)acrylic acid bonded via an ether functional group to a polyalkylene oxide-derived block (PAO), where the PAO consists of 20 to 30 alkylene oxide (AO) units, most preferably 25 AO units, where the PAO is preferably further linked via an ether functional group to a C14 to C22-aliphatic alkanol, most preferably a C16 / 18-aliphatic alkanol, where the AO is selected from EO and PO and / or BuO, more preferably EO and PO, where the amount of EO is 75, even more preferably at least 90 wt.%, most preferably essentially only EO, based on the total AO; further comprising methacrylic acid, where the ratio of the (meth)acrylate to the free methacrylic acid is from about 70 w% / 30 w% to 80 w% / 20 w%, more preferably about 75 w% / 25 w%; and

[0291] (M3) is not included.

[0292] Example 3

[0293] The dispersion according to Example 2, wherein,

[0294] (M1) the vinyl ester monomer comprises at least 90% of vinyl acetate, preferably essentially only vinyl acetate, based on the total molar amount of the vinyl ester, and

[0295] (M2) the at least one (meth)acrylate is (meth)acrylic acid bonded via an ether functional group to a polyalkylene oxide-derived block (PAO), where the PAO consists of 23 to 27 alkylene oxide (AO) units, most preferably on average 25 AO units, where the PAO is preferably further linked via an ether functional group to essentially a C16 / 18-aliphatic alkanol, most preferably a C16 / 18-aliphatic alkanol, where the AO is essentially only EO; further comprising methacrylic acid, where the ratio of the (meth)acrylate to the free methacrylic acid is from about 70 w% / 30 w% to 80 w% / 20 w%, more preferably about 75 w% / 25 w%.

[0296] Example 4

[0297] The dispersion according to Example 3, wherein,

[0298] (M1) is vinyl acetate, and

[0299] (M2) the at least one (meth)acrylate is (meth)acrylic acid bonded to a polyethylene oxide block (PEO) via an ether functional group, wherein the PEO consists of an average of 25 AO units, wherein the PEO is further connected to a C16 / 18 - aliphatic alkanol via an ether functional group, further comprising methacrylic acid, wherein the ratio of the methacrylate and the free methacrylic acid is about 75 w% / 25 w%.

[0300] Example 5

[0301] The dispersion according to any one of Examples 1 to 4, wherein,

[0302] The (CGCC) is a carboxyl - containing compound selected from carboxylated polysaccharides, more preferably carboxylated cellulose, even more preferably carboxylated methylcellulose (carboxymethylcellulose, "CMC"), and based on the total amount of monomers (M1 + M2 + M3), preferably in an amount of 2.5 to 10, most preferably about 5 weight percent.

[0303] Example 6

[0304] The dispersion according to any one of Examples 1 to 5, wherein the dispersed polymer particles have a D[4,3] value of at least 400 nm and up to 1000 nm as determined by static light scattering.

[0305] Example 7

[0306] The dispersion according to any one of Examples 1 to 6, wherein,

[0307] (S) at least one sugar and / or polysaccharide is a starch degradation product, preferably maltodextrin, and based on the total weight of monomer M, in an amount of 10 to 30, preferably 15 to 25 wt%, more preferably 17 to 23 wt%.

[0308] Example 8

[0309] The dispersion according to Example 7, wherein (S) is degraded starch having a glucose equivalent in the range of 2 to 40% according to Lane and Eynon.

[0310] Example 9

[0311] The dispersion according to Example 9, wherein (S) is maltodextrin having a DE - value of 10 to 30, preferably 12 to 16 or 25 to 30.

[0312] Example 10

[0313] The dispersion according to any one of Examples 1 to 8, wherein, as compound S, degraded starch is used, which, as measured by osmometry, has a number-average molecular weight in the range of 300 to 2000 daltons, and preferably in the range of 5 to 150, more preferably up to 70, even more preferably up to 50, and more preferably 10, even more preferably 15, and most preferably 20, each in weight percentage based on the total weight of monomers M1 + M2 + M3.

[0314] Example 11

[0315] The dispersion according to any one of Examples 1 to 10, having at least one of the following properties a) to d):

[0316] a) A transmittance of at least 20% of light with a wavelength of 525 nm when measured as a 0.01 wt% dispersion in water,

[0317] b) A pH between 2.5 and 9, preferably 3, more preferably 3.3, and more preferably up to 7, even more preferably up to 6, even more preferably up to 5, and most preferably about 3.5;

[0318] c) A density of 1.04 to 1.08 g / mL measured as a 10 wt.% dispersion (based on solids content), and

[0319] d) A viscosity of 30 to 1000 mPas (Brookfield viscosity, rotor 3; measured as a 10 wt.% - dispersion; based on solids content; concentration of 30 wt.% active substance).

[0320] Example 12

[0321] A method for producing a polymer dispersion according to any one of Examples 1 to 11, the method comprising

[0322] A) polymerizing ethylenically unsaturated monomers M, where M comprises

[0323] (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

[0324] (2) (M2) At least one (meth)acrylate optionally containing methacrylic acid as a minor component, wherein the (meth)acrylic acid in the methacrylate is bonded to a polyalkylene oxide-derived block (PAO) via an ether functional group, where the PAO consists of 2 to 40 alkylene oxides (AO), most preferably 25 AO units, and the PAO is preferably further linked via an 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 C18 - aliphatic alkanol, where the AO is preferably selected from EO, PO, and / or BuO, more preferably at least EO, with an amount of 50, more preferably at least 75, even more preferably at least 90 wt.%, most preferably essentially only EO based on the total AO; preferably containing methacrylic acid, more preferably where the ratio of the methacrylate and the free methacrylic acid is about 70 w% / 30 w% to 80 w% / 20 w%, more preferably about 75 w% / 25 w%; and

[0325] (3) (M3) Optionally, additional monomers polymerizable with M1 and M2, preferably none;

[0326] The polymerization is carried out in the presence of

[0327] - At least one emulsifier,

[0328] - Water,

[0329] -(CGCC) A carboxyl-containing compound in an amount of 1 to 15, preferably 2 to 10, more preferably 3 to 8, most preferably 4 to 6% by weight based on the total weight of monomers M, the compound being selected from compounds having at least three, more preferably at least 6, 8, 10, 15, 20, 25... carboxyl groups in their structure, where at least 10 and at most 90 percent are deprotonated (thus forming a salt with a counterion; these counterions are selected from Na, K, NH4, Mg, Ca,...), and selected from the group including: citric acid, isocitric acid; ethylenediaminetetraacetic acid; nitrilotriacetic acid; tartaric acid; oligomeric and polyacrylic acids; oligomeric and polymethacrylic acids; trimellitic acid; oligomeric amino acids with carboxyl groups, such as polyaspartic acid; oligomeric and polyglutamic acids; oligomeric and polyacetates with carboxyl groups, such as poly(glyoxylic acid) aldehyde; carboxylated oligomeric and polysaccharides, such as oxidized starch (a mixture of amylopectin, amylose); polyglucuronate; cellulose oxidized to fibroglucuronic acid; natural polycarboxylic polysaccharides, such as xylan gum; pectic acid; alginic acid; carboxymethylated polysaccharides based on 1,4 - glucan, 1,3 - glucan, 1,6 - glucan; glycuronans based on 1,4 - glucan, 1,3 - glucan, 1,6 - glucan; polygalacturonic acid; preferably carboxylated polysaccharides, more preferably carboxylated cellulose, even more preferably carboxymethylated cellulose (carboxymethyl cellulose, "CMC"); and

[0330] -(S) At least one (non-carboxylated) sugar and / or polysaccharide, such as glucose, starch degradation products, maltodextrin, in an amount of 2 to 50, preferably 5 to 35, more preferably 10 to 30, most preferably 15 to 25 wt% based on the total weight of monomer M,

[0331] Use at least one free radical initiator or free radical initiator pair, such a pair preferably comprising a peroxide and a reducing compound; such polymerization is carried out under the following conditions

[0332] - In a reaction vessel equipped with a pressurizing device and / or a device for controlling the boiling of the components, and such or such measures can hold the components in the reaction vessel during the reaction at an elevated temperature;

[0333] - At a temperature of 60 °C to 90 °C, preferably 70 °C to 80 °C;

[0334] - At a pH of up to 4, more preferably below 4, even more preferably at most 3.8, even more preferably at most 3.6;

[0335] And

[0336] B) Optionally add an additional free radical initiator or initiator pair to further reduce the content of unreacted monomer and / or reduce the color of the polymer dispersion to be obtained;

[0337] C) Optionally add at least one additional reducing compound to reduce the color of the polymer dispersion to be obtained,

[0338] D) Optionally add at least one additional additive that may be required or desired as an additional component in the polymer dispersion to be obtained;

[0339] E) Optionally carry out the step of removing the evaporable compounds from the reaction mixture by means of a distillation step and / or a stripping step using steam or a gas, preferably steam;

[0340] F) Optionally carry out the step of filtering the polymer dispersion from the previous step, preferably using a 125 micron filter;

[0341] To obtain the polymer dispersion.

[0342] Example 13

[0343] According to the method described in Example 12, wherein, for the main polymerization step, at least one persulfate is used as the free radical polymerization initiator and ascorbic acid and / or isoascorbic acid.

[0344] Example 14

[0345] The method according to embodiment 12 or 13, wherein the free radical polymerization initiator additionally comprises a transition metal.

[0346] Example 15

[0347] The method according to any one of embodiments 12 to 14, wherein for the post-polymerization step, at least one hydroperoxide and at least one sulfite are used.

[0348] Example 16

[0349] The method according to embodiment 15, wherein at least 5% of the total amount of the hydroperoxide is added after the addition of the sulfite has ended.

[0350] Example 17

[0351] The method 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 the remaining amount of one or more monomers M1 and reaction by-products and preferably substantially remove them to a level that is required or acceptable for the intended application area. This step is carried out at ambient pressure, reduced pressure or overpressure up to 2 bar absolute pressure to reduce the content of one or more organic solvents and residual volatile monomers such as vinyl esters to at most 1% by weight, preferably at most 0.5%, more preferably at most 0.01% by weight based on the total weight of the obtained polymer dispersion.

[0352] Example 18

[0353] The method according to any one of embodiments 12 to 17, wherein the dispersion is filtered to remove polymer aggregates having a size exceeding 125 microns.

[0354] Example 19

[0355] Use of an aqueous polymer dispersion as described in embodiments 1 to 11, or an aqueous polymer dispersion obtainable or obtained by any one of embodiments 12 to 18 as an emulsion component.

[0356] Example 20

[0357] Use as described in embodiment 19, which is as an emulsion component in liquid and semi-liquid compositions in the field of cleaning compositions for fabrics and hard surfaces, industrial and institutional cleaning.

[0358] Example 21

[0359] Use according to embodiment 19 or 20, wherein the composition additionally comprises at least one enzyme.

[0360] Example 22

[0361] Use according to any one of Examples 19 to 21, for imparting opacity.

[0362] Example 23

[0363] Use according to any one of Examples 19 to 22, wherein the at least one aqueous polymer dispersion is present at 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.

[0364] Example 24

[0365] Use according to any one of Examples 14 to 18, such product or composition further comprising from about 1% to about 70% by weight of a surfactant system and optionally further comprising at least one antimicrobial agent.

[0366] Example 25

[0367] A liquid or semi-liquid formulation comprising at least one aqueous polymer dispersion as defined in any one of Examples 1 to 11, or an aqueous polymer dispersion obtainable or obtained by any one of Examples 12 to 18, in an amount of from 0.01% to 10% (based on the solids content of the aqueous polymer dispersion) based on the total solids of such formulation.

[0368] Example 26

[0369] The formulation according to Example 25, which is a cleaning composition for fabrics and / or hard surfaces.

[0370] Example 27

[0371] The formulation according to any one of Examples 25 or 26, which is a laundry detergent, cleaning composition or fabric and home care product comprising at least one aqueous polymer dispersion for imparting opacity.

[0372] Example 28

[0373] The formulation according to any one of Examples 25 to 27, which further comprises from about 1% to about 70% by weight of a surfactant system and optionally comprises at least one antimicrobial agent and / or at least one enzyme.

[0374] Example 29

[0375] The formulation according to any one of Examples 25 to 28, which further comprises 2-phenoxyethanol as an antimicrobial agent, preferably in an amount ranging from 2 ppm to 5%, more preferably comprising from 0.1% to 2%, all based on the weight of the composition.

[0376] Example 30

[0377] The formulation according to any one of Examples 25 to 29, further comprising 4,4'-dichlor-2-hydroxy-diphenyl ether in 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.

[0378] Example 31

[0379] A method of preserving the formulation according to any one of Examples 25 to 30 against microbial contamination or growth, the method comprising adding 2-phenoxyethanol as an antimicrobial agent to the composition, which is an aqueous composition comprising water as a solvent.

[0380] Example 32

[0381] A method of washing a fabric or cleaning a hard surface, the method comprising treating the fabric or hard surface with the formulation according to any one of Examples 25 to 29, which formulation comprises 4,4'-dichlor-2-hydroxy-diphenyl ether, preferably comprising 4,4'-dichlor-2-hydroxy-diphenyl ether in 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.

[0382] The following examples should further illustrate the invention without limiting the scope of the invention.

[0383] Examples

[0384] NTU value: See table, determined in liquid detergent

[0385] Example overview

[0386] General formulation

[0387]

[0388]

[0389] 1) For additional examples vary the amounts and ingredients according to the table shown below (if there are deviations in the amounts given in the table compared to the general formulation).

[0390] General process description

[0391] 1. Heat the pre-feed to an internal temperature of 60 / 70 °C at 120 upm under nitrogen

[0392] 2. At the temperature, add 5% of Feed 1 within 1 min and wait for 5 min

[0393] 3. Start feeding 2 (4 h 15 min) and feeding 3 (4 h 15 min)

[0394] 4. After 15 min of feeding 2 and feeding 3, start the remaining feeding 1 (3 h 30 min)

[0395] 5. When feeding 2 and feeding 3 are completed, add feeding 4 (1 min) and wait for 5 min

[0396] 6. Start feeding 5 (1 h 30 min)

[0397] 7. After feeding 5 has been waiting for 30 min, then add feeding 6 (1 min)

[0398] 8. Wait for 30 min

[0399] 9. Cool to an internal temperature of 23 °C

[0400] 10. When filling the filter, conduct a test using a 125 μm filter

[0401] Apparatus

[0402] - 4 L cylindrical glass reactor

[0403] - V4A round anchor stirrer

[0404] - Weight metering module

[0405] - Heating bath

[0406] Detailed description of the general recipe:

[0407] At RT (23 °C), charge the reactor with the initial feed, which consists of demineralized water, Finnfix 10 (carboxymethyl cellulose), and sodium acetate as a buffer. Thereafter, heat the mixture to 70 °C with stirring under a N2 atmosphere.

[0408] For feeding 1, mix demineralized water with demineralized water, Disponil FES27, vinyl acetate, and Visiomer C18PEG 1105MA W. To produce an emulsion, mix the feed using a homogenizer.

[0409] At 70 °C, add 5% of feeding 1 within 1 minute. Then stir the mixture for 5 minutes.

[0410] Thereafter, add feeding 2, 7% sodium persulfate solution, and feeding 3, 2% ascorbic acid solution, over 4 h 30 min. After 30 min of feeding 2 and 3, add the remaining 95% of feeding 1 over 3 h 30 min.

[0411] When feeds 2 and 3 are complete, stir for 10 minutes. Then add feed 4, tert-butyl hydroperoxide all at once and add feed 5, 2.5% sodium bisulfite acetone solution as a chemical deodorant over 1 hour 30 minutes. Cool to room temperature after feed 5. Filter the final product through a 125 μm nylon filter.

[0412]

[0413]

[0414]

[0415]

[0416] Determination of opacity:

[0417] The light transmittance (LD value) is measured at 525 nm in a 1 cm cuvette using a photometer. Turbidity measurement is carried out using a device from Hanna (turbidimeter HI88703 for nephelometric turbidity measurement) to provide NTU values.

[0418] LD: 1 cm cuvette, 0.01% water; 525 nm

[0419] Particle size: Malvern; D[0.5] 50% of the particles

[0420] Turbidity by light scattering method: nephelometric turbidity unit (NTU); formazin scale.

[0421] pH measurement: Pour the dispersion into a 250 ml beaker and connect the pH electrode (combination electrode) of the Knick Portamess meter at 25 °C and measure the pH. The measurement is carried out for 15 seconds until a constant pH value is reached.

[0422] Viscosity: Brookfield SP3, 25 rpm; 30% solids content dispersion

Claims

1. An aqueous polymer dispersion obtainable by free radical aqueous emulsion polymerization of a mixture comprising a) ethylenically unsaturated monomers M, where M comprises (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)acrylate optionally comprising methacrylic acid as a minor component, wherein the (meth)acrylic acid in the methacrylate is bonded via an ether functional group to a block derived from a polyalkylene oxide (PAO), where the PAO consists of 2 to 40 alkylene oxide (AO) units, most preferably 25 AO units, where the PAO is preferably further linked via an 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 C18 - aliphatic alkanol, where the AO is preferably selected from EO, PO and / or BuO, more preferably at least EO, in an amount of 50, more preferably at least 75, even more preferably at least 90 wt.%, most preferably essentially only EO, based on the total AO; preferably comprising methacrylic acid, more preferably where the ratio of the methacrylate and the free methacrylic acid is from about 70 w% / 30 w% to 80 w% / 20 w%, more preferably about 75 w% / 25 w%; (3) (M3) optionally additional monomers copolymerizable with M1 and M2, preferably none; b) (CGCC) 1 to 15, preferably 2 to 10% by weight, based on the total weight of monomers M, of a carboxyl - containing compound selected from compounds having at least three carboxyl groups in their structure, where at least 10 and at most 90 percent are deprotonated, selected from the group comprising: citric acid, isocitric acid; ethylenediaminetetraacetic acid; nitrilotriacetic acid; tartaric acid; oligomeric and polyacrylic acids; oligomeric and polymethacrylic acids; trimellitic acid; oligomeric amino acids having carboxyl groups, such as polyaspartic acid; oligomeric and polyglutamic acids; oligomeric and polyacetates having carboxyl groups, such as poly(glyoxylic acid) aldehyde; carboxylated oligomeric and polysaccharides, such as oxidized starch (a mixture of amylopectin, amylose); polyglucuronates; cellulose oxidized to glucuronic acid; natural polycarboxylic polysaccharides, such as xylan; pectic acid; alginic acid; carboxymethylated polysaccharides based on 1,4 - glucans, 1,3 - glucans, 1,6 - glucans; glycuronans based on 1,4 - glucans, 1,3 - glucans, 1,6 - glucans; polygalacturonic acid; preferably carboxylated polysaccharides, more preferably carboxylated cellulose, even more preferably carboxymethyl cellulose ("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, preferably 5 to 35 wt%, based on the total weight of monomers M, and d) at least one emulsifier selected from non - ionic and anionic surfactants, e) optionally sulfate ions, and f) optionally sulfite ions, Preferably, the amount of M1 is 80 to 99.99 mol%, and the amount of M2 is 0.01 to 20 mol%, and preferably at most 10, even more preferably at most 5, still more preferably at most 2%. The total amount of M1 and M2 is 100 weight percent, and the dispersion has a pH of up to 4 after the polymerization is completed.

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

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

4. The dispersion according to claim 3, wherein (M1) is vinyl acetate, and (M2) the at least one (meth)acrylate is (meth)acrylic acid bonded to a polyethylene oxide block (PEO) via an ether functional group, where the PEO consists of an average of 25 AO units. The PEO is further connected to a C16 / 18 aliphatic alkanol via an ether functional group, and further contains methacrylic acid, and the ratio of the methacrylate to the free methacrylic acid is about 75 w% / 25 w%.

5. The dispersion according to any one of claims 1 to 4, wherein The (CGCC) is a carboxyl group-containing compound selected from carboxylated polysaccharides, more preferably carboxylated cellulose, even more preferably carboxylated methylcellulose (carboxymethylcellulose, "CMC"), and based on the total amount of monomers (M1 + M2 + M3), its amount is preferably 2.5 to 10, most preferably about 5 weight percent.

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

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

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

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

10. A method for producing a polymer dispersion according to any one of claims 1 to 9, the method comprising A) polymerizing ethylenically unsaturated monomers M, where M comprises (1) (M1) at least one vinyl ester, preferably comprising vinyl acetate, more preferably comprising at least 50%, even more preferably at least 90% of vinyl acetate, and (2) (M2) at least one (meth)acrylate optionally containing methacrylic acid as a minor component, wherein the (meth)acrylic acid in the methacrylate is bonded to a polyalkylene oxide-derived block (PAO) through an ether functional group, where the PAO consists of 2 to 40 alkylene oxide (AO) units, most preferably 25 AO units, and where the PAO is preferably further connected through an 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 C18 - aliphatic alkanol, and where the AO is preferably selected from EO, PO, and / or BuO, more preferably at least EO, and based on the total AO, its amount is 50, more preferably at least 75, even more preferably at least 90 wt.%, most preferably consisting essentially of only EO; preferably comprising methacrylic acid, more preferably where the ratio of the methacrylate to the free methacrylic acid is about 70 w% / 30 w% to 80 w% / 20 w%, more preferably about 75 w% / 25 w%; and (3) (M3) optionally additional monomers polymerizable with M1 and M2, preferably none; The polymerization is carried out in the presence of - at least one emulsifier, - water, -(CGCC) A carboxyl-containing compound in an amount of 1 to 15, preferably 2 to 10, more preferably 3 to 8, and most preferably 4 to 6% by weight, based on the total weight of monomer M. The compound is selected from compounds having at least three, more preferably at least 6, 8, 10, 15, 20, 25 or more carboxyl groups in its structure, where at least 10 and at most 90% are deprotonated - and thus form salts with counterions; these counterions are selected from Na, K, NH4, Mg, Ca - selected from the group including: citric acid, isocitric acid; ethylenediaminetetraacetic acid; nitrilotriacetic acid; tartaric acid; oligomeric and polyacrylic acids; oligomeric and polymethacrylic acids; trimellitic acid; oligomeric amino acids having carboxyl groups, such as polyaspartic acid; oligomeric and polyglutamic acids; oligomeric and polyacetates having carboxyl groups, such as poly(glyoxylic acid) aldehyde; carboxylated oligomeric and polysaccharides, such as oxidized starch, such as a mixture of amylopectin, amylose; polyglucuronate; cellulose oxidized to glucuronic acid; natural polycarboxylic polysaccharides, such as xylan; pectic acid; alginic acid; carboxymethylated polysaccharides based on 1,4-glucan, 1,3-glucan, 1,6-glucan; glycuronan based on 1,4-glucan, 1,3-glucan, 1,6-glucan; polygalacturonic acid; preferably carboxylated polysaccharides, more preferably carboxylated cellulose, even more preferably carboxymethyl cellulose ("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, preferably 5 to 35, more preferably 10 to 30, and most preferably 15 to 25 wt% based on the total weight of monomer M, using at least one free radical initiator or free radical initiator pair, such a pair preferably comprising a peroxide and a reducing compound, more preferably at least one persulfate as a free radical polymerization initiator and ascorbic acid and / or isoascorbic acid, This polymerization is carried out under the following conditions - In a reaction vessel equipped with a pressurizing device and / or a device for controlling the boiling of the components, and such measures or such measures can hold the components in the reaction vessel during the reaction at an elevated temperature; - At a temperature of 60°C to 90°C, preferably 70°C to 80°C; - At a pH of up to 4, more preferably less than 4, even more preferably at most 3.8, and even more preferably at most 3.6; and B) Optionally adding an additional free radical initiator or initiator pair to further reduce the content of unreacted monomer and / or reduce the color of the polymer dispersion to be obtained; C) Optionally adding at least one additional reducing compound to reduce the color of the polymer dispersion to be obtained; D) Optionally adding at least one additional additive that may be required or desired as an additional component in the polymer dispersion to be obtained; E) Optionally carrying out the step of removing evaporable compounds from the reaction mixture by means of a distillation step and / or a stripping step using steam or gas, preferably steam; F) Optionally carrying out the step of filtering the polymer dispersion from the previous step, preferably using a 125 micron filter; to obtain the polymer dispersion.

11. The method according to claim 10, wherein, The free radical polymerization initiator additionally comprises a transition metal.

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 are used.

13. The method according to claim 12, wherein, At least 5% of the total amount of the hydroperoxide is added after the addition of the sulfite has ended.

14. Use of an aqueous polymer dispersion as defined in claims 1 to 9, or an aqueous polymer dispersion obtainable or obtained by any one of claims 10 to 13 as an emulsion component, preferably in the field of cleaning compositions as an emulsion component in liquid and semi-liquid compositions for fabric and hard surface, industrial and institutional cleaning. wherein the at least one aqueous polymer dispersion is present at a concentration of from about 0.01% to about 10% by weight, based on the total weight of such compositions or products (based on the solids content of the aqueous polymer dispersion), Preferably, the composition further meets at least one of the following requirements: a. comprises at least one enzyme, which is preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, mannanases, hemicellulases, phospholipases, esterases, xylanases, deoxyribonucleases, dispersases, pectinases, redox enzymes, cutinases, lactases and peroxidases, more preferably at least two of the foregoing types, and in the case of containing an enzyme, preferably also contains at least one enzyme stabilization system, b. comprises a surfactant system of from about 1% to about 70% by weight, c. comprises an effective amount of at least one additional cleaning aid, and d. exhibits improved washing performance, preferably in primary cleaning.

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 by any one of claims 10 to 14, in an amount of 0.01% to 10% based on the total solids of such formulation (based on the solids content of the aqueous polymer dispersion), optionally further comprising at least one of a) to c) a. at least one enzyme, which is preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, mannanases, hemicellulases, phospholipases, esterases, xylanases, deoxyribonucleases, dispersases, pectinases, redox enzymes, cutinases, lactases and peroxidases, more preferably at least two of the foregoing types, and in the case of containing an enzyme, preferably also contains at least one enzyme stabilization system, b. a surfactant system of from about 1% to about 70% by weight, c. an effective amount of at least one additional cleaning aid, preferably a cleaning composition or a fabric and household care product, more preferably a cleaning composition, more preferably a laundry detergent or a dishwashing detergent, even more preferably a concentrated liquid detergent formulation, a single-dose single-load laundry detergent formulation, a liquid manual dishwashing detergent formulation, most preferably a liquid laundry detergent formulation or a liquid manual dishwashing detergent formulation, Optionally further comprising at least one antimicrobial agent, preferably 2-phenoxyethanol, in an amount ranging from 2 ppm to 5%, more preferably from 0.1% to 2%, by weight of the composition, and Optionally containing 4,4'-dichloro-2-hydroxy diphenyl ether at a concentration of from 0.001% to 3%, preferably from 0.002% to 1%, more preferably from 0.01% to 0.6% - each by weight of the composition.

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