JP2025538542A - Aqueous polymer dispersions suitable as opacifiers in liquid formulations, manufacturing process and their use - Patents.com - Google Patents

Abstract

The present invention relates to an aqueous polymer dispersion suitable as an opacifier in liquid formulations, a manufacturing process, the use of such an aqueous polymer dispersion in a cleaning composition, and such a composition. The aqueous polymer dispersion can be obtained by radical emulsion polymerization in an aqueous environment by polymerizing i) at least one vinyl ester, ii) at least one (meth)acrylic acid ester (which may optionally contain methacrylic acid as a minor component, the (meth)acrylic acid in the methacrylic acid ester being linked via an ether functional group to a polyalkylene oxide derived block (PAO), the PAO consisting of 2 to 40 alkylene oxides (AOs)), and iii) optionally further polymerizable monomers in the presence of a) a carboxyl group-containing compound selected from compounds having in its structure at least three carboxyl groups, at least 10 percent and at most 90 percent of which are deprotonated, b) at least one carboxylated or non-carboxylated sugar and/or carboxylated or non-carboxylated polysaccharide, and c) at least one emulsifier selected from nonionic and anionic surfactants. The resulting aqueous polymer dispersion optionally also contains sulfate and/or sulfite ions.
[Selection diagram] None

Description

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

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

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

Due to climate change, one of the most important goals of the current detergent and cleaning (D&C) industry is to significantly reduce CO2 emissions per wash by improving cold water conditions, for example by improving cleaning efficiency at low temperatures below 40, 30, or 20°C, or even lower, reducing the amount of chemicals used per wash, increasing the weight efficiency of cleaning technologies, reducing the amount of water used per wash, introducing bio-based ingredients, etc. Therefore, one important goal of the D&C industry is the need to improve the sustainability of cleaning formulations, especially by improving efficiency at low temperatures and reducing the amount of water required (especially in laundry and dishwashing formulations), as well as avoiding the accumulation of non-degradable compounds in the ecosystem. There is a high desire in the industry and by consumers to reduce such CO2 emissions or improve the "footprint" of any product, and there has been growing interest in its origin, such as from natural or renewable resources, or in its manufacture in relation to production efficiency and therefore reduced energy usage, both compared to conventional products, in its efficiency of use, such as the same performance at lower amounts or higher performance at the same usage level, and even more so in its persistence in the natural environment during and/or after its use, such as biodegradation.

As a result of these trends, there is a strong need for new biodegradable cleaning additives that provide at least equivalent cleaning properties and a reduced CO2 footprint by being bio-based, biodegradable, or even both. The materials should preferably exhibit good primary cleaning activity, soil removal against oily/greasy and particulate stains, and/or improve whiteness retention, thus also minimizing the amount of suspended and emulsified oily/greasy and particulate stains that redeposit on fabrics or hard surfaces, etc.

Therefore, there is a need to provide compounds that are biodegradable but have at least the same performance as known, but non-biodegradable compounds. Such biodegradability is measured within 28 days under specified conditions, as required by many users, particularly in the detergent technology field, and as a future legal requirement in several countries and regions around the world.

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

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

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

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

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

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

D6 (JP 59155411 A, Nippon Synthetic Chemical Industry, JP 1983-028686 A) describes a copolymer of an oxyalkylene group-containing unsaturated monomer and vinyl acetate in solution polymerization in alcohol. The copolymerization of vinyl acetate includes an oxyalkylene group-containing unsaturated monomer (such as methacrylic acid). The number of oxyalkylene groups, i.e., n, is advantageously 1 to 50, preferably about 3 to 50. The oxoalkylene group may terminate with an alkyl. A preferred example is allylpolyoxoethylene, with one example being (10EO)-oxoethylene methacrylate. The modified vinyl acetate resin 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, among other applications. No biodegradation results have been published. The use of polycarboxylates such as carboxymethyl cellulose to improve biodegradability is not disclosed.

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

A terpolymer consisting of vinyl alcohol, vinyl acetate, and alkylpolyoxoethylene methacrylate ester is claimed in D8 (EP 199358 to Celanese Corp). The fabric protector comprises at least 50% vinyl alcohol in the terpolymer. The terpolymer is used as a barrier layer in a thermoplastic process for packaging articles. No biodegradation results have been published. The use of polycarboxylates such as carboxymethyl cellulose to improve biodegradability is not disclosed.

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

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

As a result of these trends, there is a strong need for new biodegradable cleaning additives that provide at least equivalent cleaning properties and a reduced CO2 footprint by being bio-based, biodegradable, or even both. The materials should preferably exhibit good primary cleaning activity, soil removal against oily/greasy and particulate stains, and/or improve whiteness retention, thus also minimizing the amount of suspended and emulsified oily/greasy and particulate stains that redeposit on fabrics or hard surfaces, etc.

It was therefore an object to provide an opacifier for compositions such as detergent, cleaning and/or fabric and home care compositions/formulations that has improved biodegradability.

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

The aqueous dispersions of the present invention, obtainable or obtained by the process according to the present invention, can be used as opacifiers in certain compositions, such as detergent, cleaning and/or fabric and home care compositions/formulations.

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

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

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

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

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

Similarly, the terms "substantially free of..." or "substantially free from..." or "essentially (containing/comprising)..." may be used herein; this means that the indicated material is at the very minimum not intentionally added to form part of the composition, or preferably is not present at analytically detectable levels. It is meant to encompass compositions in which the indicated material is present only as an impurity in one of the other intentionally included materials. The indicated material may be present, if at all, at levels of less than 1%, or even less than 0.1%, or even less than 0.01%, or even 0% by weight of the composition.

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

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

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

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

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

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

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

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

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

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

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

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

pH measurements are performed as described in the experimental section.

Throughout this specification, the term "compound of the present invention" may be used in place of "(aqueous) dispersion of the present invention" and "(aqueous) dispersion of this (present) invention" to mean that the compound is disclosed herein as the present invention, is defined by its structure and/or its manufacturing process, and/or can be obtained by the process defined herein.

The definitions and preferences given in the "Definitions" section above are included as part of the present invention, as described herein below.

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

Specifically, the present invention provides the following:
a) an ethylenically unsaturated monomer M,
(1) (M1) at least one vinyl ester, preferably comprising vinyl acetate, more preferably comprising at least 50%, even more preferably at least 90%, of vinyl acetate; and (2) (M2) at least one (meth)acrylic acid ester, optionally comprising as a minor component methacrylic acid, wherein the (meth)acrylic acid in the methacrylic acid ester is linked via an ether functional group to a polyalkylene oxide derived block (PAO), the PAO consisting of 2 to 40 alkylene oxide (AO), most preferably 25 AO-units, the PAO preferably comprising C1 to C24, preferably at least C4, alkylene oxides via the ether functional group. more preferably further bonded to at least a C6, even more preferably a C8-C24-aliphatic alkanol, most preferably a C18-aliphatic alkanol, wherein AO is preferably selected from EO, PO and/or BuO, more preferably at least EO in an amount of from 50 wt. %, more preferably at least 75 wt. %, even more preferably at least 90 wt. %, most preferably essentially EO only, based on total AO; preferably comprising methacrylic acid, more preferably methacrylic acid ester and free methacrylic acid in a ratio of about 70 wt. %/30 wt. %-80 wt. %/20 wt. %, more preferably about 75 wt. %/25 wt. %;
(3) (M3) Optional further monomers (preferably absent) that are polymerizable with M1 and M2.
an ethylenically unsaturated monomer M comprising:
b) 1 to 15 wt. %, preferably 2 to 10 wt. %, more preferably 3 to 8 wt. %, and most preferably 4 to 6 wt. %, based on the total weight of the (CGCC) monomer M, of a carboxyl group-containing compound selected from compounds having at least 3, more preferably at least 6, 8, 10, 15, 20, 25 or more carboxyl groups in their structure, with at least 10 percent and at most 90 percent of the carboxyl groups being deprotonated (and thus Na , K, NH4, Mg, Ca), citric acid, isocitric acid; ethylenediaminetetraacetic acid; nitriloacetic acid; tartaric acid; oligomeric and polyacrylic acids; oligomeric and polymethacrylic acids; trimellitic acid; oligomeric amino acids having carboxy groups such as polyaspartic acid; oligomeric and polyglutamic acid; oligomeric and polyacetates having carboxy groups such as poly(glyoxylic)aldehyde; oxidized starch (amylopectin, amylose, carboxylated oligomeric and polymeric saccharides such as carboxylated celluloses (mixtures of celluloses); polyglucuronates; celluloses oxidized to celluronates; natural polycarboxylic polysaccharides such as xylans; pectinic acid; alginic acid; carboxymethylated polysaccharides based on 1,4-, 1,3-, and 1,6-polyglucans; polyuronic acids based on 1,4-, 1,3-, and 1,6-polyglucans; polygalacturones; carboxyl group-containing compounds, preferably selected from the group comprising carboxylated polysaccharides, more preferably carboxylated celluloses, and even more preferably carboxylated methylcellulose (carboxymethylcellulose, "CMC"); and c) at least one (non-carboxylated) saccharide and/or polysaccharide, such as glucose, starch degradation products, maltodextrins, in an amount of 2 to 50% by weight, preferably 5 to 35% by weight, more preferably 10 to 30% by weight, and most preferably 15 to 25% by weight, based on the total weight of the (S) monomer M,
and d) at least one emulsifier selected from nonionic and anionic surfactants,
i) at least one nonionic surfactant,
anionic emulsifiers having at least one anionic group selected from phosphate, phosphonate, sulfate and sulfonate groups;
anionic emulsifiers, typically used in the form of their alkali metal salts, in particular their sodium salts, or in the form of their ammonium salts;
Preferably, anionic emulsifiers having at least one sulfate or sulfonate group or at least one phosphate or phosphonate group, more preferably having at least one sulfonate or sulfate group, most preferably having only one sulfonate or one sulfate group,
i) a) The anionic emulsifier having at least one sulfate or sulfonate group is preferably
salts of alkyl sulfates, in particular C8 to C22 alkyl sulfates, in particular alkali metal and ammonium salts,
the salts, in particular alkali metal and ammonium salts, of sulfuric acid monoesters of C2-C3 alkoxylated alkanols, in particular of sulfuric acid monoesters of C2-C3 alkoxylated C8-C22 alkanols, preferably having a C2-C3 alkoxylation level (AO level) ranging from 2 to 40;
- sulfuric acid monoesters of C2-C3 alkoxylated alkylphenols, in particular the salts of sulfuric acid monoesters of C2-C3 alkoxylated C4-C18-alkylphenols, in particular the alkali metal and ammonium salts (AO level preferably 3-40),
salts, especially alkali metal and ammonium salts, of alkylsulfonic acids, in particular C8-C22-alkylsulfonic acids,
dialkyl esters, in particular salts of di-C4 to C18-alkyl esters of sulfosuccinic acid, in particular alkali metal and ammonium salts,
- the salts, in particular the alkali metal and ammonium salts, of alkylbenzenesulfonic acids, in particular C4-C22 alkylbenzenesulfonic acids, and - the salts, in particular the alkali metal and ammonium salts, of mono- or disulfonated alkyl-substituted diphenyl ethers, for example bis(phenylsulfonic acid) ethers having a C4-C24 alkyl group on one or both aromatic rings;
(The term "C2-C3 alkoxylated" means that the compound is ethoxylated, propoxylated or coethoxylated/propoxylated, i.e., that the compound is obtained by a process that introduces polyethylene oxide, polypropylene oxide or poly(ethylene oxide-co-propylene oxide) groups, respectively.)
Selected from:
i) b) The anionic emulsifier having at least one phosphate or phosphonate group is preferably
salts, especially alkali metal and ammonium salts, of mono- and dialkyl phosphates, in particular C8-C22-alkyl phosphates,
- phosphoric acid monoesters of C2-C3-alkoxylated alkanols, preferably having an alkoxylation level in the range from 2 to 40, in particular in the range from 3 to 30, for example phosphoric acid monoesters of ethoxylated C8-C22 alkanols, preferably having an ethoxylation level (EO level) in the range from 2 to 40, phosphoric acid monoesters of propoxylated C8-C22 alkanols, preferably having a propoxylation level (PO level) in the range from 2 to 40, and salts, in particular alkali metal and ammonium salts, of phosphoric acid monoesters of ethoxylated-co-propoxylated C8-C22 alkanols, preferably having an ethoxylation level (EO level) in the range from 1 to 20 and a propoxylation level of 1 to 20,
salts of phosphoric acid monoesters of C2-C3-alkoxylated alkylphenols, in particular the salts of phosphoric acid monoesters of C2-C3-alkoxylated C4-C18-alkylphenols, in particular the alkali metal and ammonium salts (AO level preferably 3-40),
- the salts, in particular of C8-C22-alkylphosphonic acids, of which the alkali metal and ammonium salts are preferred, and - the salts, in particular of C4-C22-alkylbenzenephosphonic acids, of which the alkali metal and ammonium salts are preferred;
More preferred anionic emulsifiers are those from the following group:
salts of alkyl sulfates, in particular C8 to C22 alkyl sulfates, in particular alkali metal and ammonium salts,
salts, especially alkali metal salts, of sulfuric acid monoesters of C2-C3-alkoxylated alkanols, in particular of sulfuric acid monoesters of C2-C3-alkoxylated C8-C22-alkanols, preferably having an AO level in the range from 2 to 40;
sulfuric acid monoesters of C2-C3-alkoxylated alkylphenols, in particular those of C2-C3-alkoxylated C4-C18-alkylphenols (AO level preferably 3-40),
alkylbenzenesulfonic acids, in particular C4-C22 alkylbenzenesulfonic acids, and for example mono- or disulfonated alkyl-substituted diphenyl ethers of bis(phenylsulfonic acid) ethers having a C4-C24 alkyl group on one or both aromatic rings;
ii) at least one nonionic surfactant,
for example,
C2-C3-alkoxylated mono-, di- and trialkylphenols, in which the number of repeating units of the alkylene oxide derived moiety is preferably from 3 to 50 and/or the alkyl groups are preferably C4-C10-alkyl;
- C2-C3 alkyloxates of long-chain alcohols, such as ethoxylates, propoxylates or ethoxylate-co-propoxylates, in which the number of repeating units of the alkylene oxide-derived moiety is preferably between 3 and 100 and/or the alkyl group is preferably C8-C36-alkyl, and - polyethylene oxide/polypropylene oxide homo- and copolymers, which may comprise alkylene oxide units copolymerized in random distribution or in the form of blocks or mixtures of homoblocks and random blocks,
More preferably, emulsifiers selected from aromatic aliphatic or aliphatic nonionic emulsifiers selected from those having alkyl groups C8-C30 with an average alkoxylation level of 5 to 100, particularly preferably those having linear C12-C20 alkyl groups and an average alkoxylation level of 10 to 50, C2-C3-alkoxylated monoalkylphenols, and C2-C3-alkoxylated long-chain alkanols;
and an aqueous polymer dispersion obtainable by radical aqueous emulsion polymerization of a mixture comprising e) optionally sulfate ions, and f) optionally sulfite ions, wherein preferably the amount of M1 is 80 to 99.99 mol %, more preferably the amount of M1 is at least 98%, the amount of M2 is 0.01 to 20 mol %, more preferably 0.1, even more preferably 0.2, even more preferably 0.5, most preferably 0.7, preferably at most 10, even more preferably at most 5, more preferably at most 2%, most preferably the amount of M1 is about 99 wt %, the amount of M2 is about 1 wt %, and the total amount of M1+M2 is 100 wt %, and wherein the dispersion has, after completion of the polymerization, a pH of at most 4, more preferably less than 4, even more preferably at most 3.8, even more preferably at most 3.6, more preferably at least 2.5, even more preferably at least 3, even more preferably at least 3.2, most preferably at least 3.4.

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

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

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

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

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

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

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

CGCC is believed to be able to interact with polymerized moieties derived from at least one monomer M2 within the polymer product dispersed in the dispersion. Such interactions appear to provide superior compatibility and stability to the dispersion; they also favor attacks on the chemical structure, thus resulting in the observed high biodegradation rates of the aqueous polymer dispersions, which are higher than those of dispersions that do not contain the carboxyl-containing compound (CGCC).

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

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

In preferred variations of the above two embodiments, (S) is a maltodextrin having a DE value of 10 to 30, preferably 12 to 16 or 25 to 30.

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

Such degraded starches can be obtained by known means, such as chemical degradation, catalytic degradation using a suitable catalyst or enzymes. In this specification, (S) is preferably derived from enzymatic degradation, as this is a clean and rapid approach that essentially does not involve chemical residues from the degradation reaction in the degradation products (other than starch and sugars derived from starch).

Furthermore, the use of maltodextrin provides increased stability at lower storage temperatures for the dispersions of the present invention.

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

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

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

As a result of the polymerization reaction, the aqueous dispersion may contain sulfites and/or sulfates, primarily resulting from the use of persulfate initiators.

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

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

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

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

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

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

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

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

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

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

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

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

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

Another subject of the present invention is therefore a cleaning composition, fabric care and home care product, preferably a laundry cleaning composition, laundry treatment product or laundry care product or laundry cleaning product, preferably a liquid laundry detergent formulation or liquid laundry detergent product, comprising at least one aqueous polymer dispersion as detailed herein above and/or an aqueous polymer dispersion obtainable from the process as detailed herein above, wherein such composition or product exhibits improved opacity.

Such compositions or products of the present invention include at least one aqueous polymer dispersion as detailed hereinabove and/or an aqueous polymer dispersion obtainable from the process detailed hereinabove, such polymer dispersions having polymer structures similar to those described hereinabove in all of their embodiments, variants, and preferred, more preferred, etc. embodiments, as detailed hereinabove.

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

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

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

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.

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

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

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

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

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

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

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

The selection of additional surfactants and further cleaning adjuncts in these embodiments can depend on the application and desired benefits.

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

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

Compositions and formulations for industrial and institutional cleaning include those designed to clean any type of soiled material or surface, such as hard surface cleaners for any type of surface, including tiles, carpets, PVC surfaces, wooden surfaces, metal surfaces, lacquered surfaces, etc.

The cleaning composition comprises a surfactant system in an amount sufficient to impart 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% surfactant system by weight of the composition. In further embodiments, the cleaning composition comprises from about 5% to about 30% surfactant system by weight of the composition. The surfactant system may include a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, and combinations thereof. Those skilled in the art will understand that a detersive surfactant includes any surfactant or surfactant mixture that aids in the cleaning, stain removal, or laundering of soiled materials.

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

Such cleaning compositions, their components, their general composition, and more specific compositions are all known and are shown, for example, in publications 800542 and 800500 published by Protegas, Liechtenstein, and in WO 2022/136409 and WO 2022/136408. The opacifying compounds, if actually used or merely intended to be used therein, can be partially or completely replaced by the aqueous polymer dispersions of the present invention; if not utilized, the aqueous polymer dispersions of the present invention can be added in the amounts indicated herein. These aforementioned documents also disclose various types of formulations for cleaning compositions, and all types of such compositions are equally applicable to the cleaning compositions contemplated herein.

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

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

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

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

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

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

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

The composition can be enclosed in a single- or multi-compartment pouch. A multi-compartment pouch can have at least two, at least three, or at least four compartments. A multi-compartment pouch includes compartments that are side-by-side and/or nested. The composition contained in the pouch or its compartments can be a liquid, a solid (such as a powder), or a combination thereof.

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

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

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

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

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

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

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

Suitable examples of such cleaning adjuvants and their amounts of use are described, for example, in WO 99/05242, U.S. Pat. Nos. 5,576,282, 6,306,812 B1, and 6,326,348 B1.

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

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

In addition to the surfactant system and graft polymer, the liquid cleaning composition may additionally comprise, and preferably comprises at least one of, a rheology control/adjusting agent, an emollient, a moisturizer, a skin rejuvenation active, and a solvent.

The solid composition may additionally contain, and preferably contains at least one of, a filler, a bleaching agent, a bleach activator, and a catalytic material.

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

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

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

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

The cleaning compositions of the present invention may comprise, in addition to all other ingredients mentioned, one or more enzymes, more preferably a protease and/or amylase, selected from those disclosed hereinabove; even more preferably, the protease is a protease having at least 90% sequence identity to SEQ ID NO: 22 of EP 1921147 B1 and having the amino acid substitution R101E (according to BPN' numbering), and the amylase is an amylase having at least 90% sequence identity to SEQ ID NO: 54 of WO 2021032881 A1; such enzymes are preferably present in the formulation at a level of from about 0.00001% to about 5% by weight of enzyme protein, preferably from about 0.00001% to about 2% by weight, more preferably from about 0.0001% to about 1% by weight, or even more preferably from about 0.001% to about 0.5% by weight, based on the weight of the composition.

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

(In all weight percentages below; if the ingredient is added as a solution or dispersion, the percentage refers to the active substance content, i.e., typically the solids content of the ingredient in such solution or dispersion.)

The liquid laundry detergent according to the present invention comprises:
0.05 to 5% of at least one aqueous polymer dispersion (% by solids);
0.05 to 10% of at least one cleaning polymer;
1 to 50% surfactant;
0.1 to 40% of a builder, cobuilder and/or chelating agent;
0.1 to 50% of other adjuvants;
It is made up of water to make up 100%.

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

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

The liquid hand dish detergent according to the present invention comprises:
0.05 to 5% of at least one dispersion of the present invention;
1 to 50% surfactant;
0.1 to 50% of other adjuvants;
It is made up of water to make up 100%.

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

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

In all three tables above: * (60% by weight of vinyl acetate grafted onto polyethylene glycol with an Mn of 6,000 g/mol as the graft substrate (based on the total weight of the polymer; produced according to the general disclosure of WO 2007138054 A1))

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

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

Most Preferred Embodiments Embodiment 1
below,
a) an ethylenically unsaturated monomer M,
(1) (M1) at least one vinyl ester, preferably comprising vinyl acetate, more preferably comprising at least 50%, even more preferably at least 90%, of vinyl acetate; and (2) (M2) at least one (meth)acrylic acid ester, optionally comprising as a minor component methacrylic acid, wherein the (meth)acrylic acid in the methacrylic acid ester is linked via an ether functional group to a polyalkylene oxide derived block (PAO), the PAO consisting of 2 to 40 alkylene oxide (AO), most preferably 25 AO-units, the PAO preferably comprising C1 to C24, preferably at least C4, alkylene oxides via the ether functional group. more preferably further bonded to at least a C6, even more preferably a C8-C24-aliphatic alkanol, most preferably a C18-aliphatic alkanol, wherein AO is preferably selected from EO, PO and/or BuO, more preferably at least EO in an amount of from 50 wt. %, more preferably at least 75 wt. %, even more preferably at least 90 wt. %, most preferably essentially EO only, based on total AO; preferably comprising methacrylic acid, more preferably methacrylic acid ester and free methacrylic acid in a ratio of about 70 wt. %/30 wt. %-80 wt. %/20 wt. %, more preferably about 75 wt. %/25 wt. %;
(3) (M3) Optional further monomers (preferably absent) that are polymerizable with M1 and M2.
an ethylenically unsaturated monomer M comprising:
b) 1 to 15 wt. %, preferably 2 to 10 wt. %, more preferably 3 to 8 wt. %, and most preferably 4 to 6 wt. %, based on the total weight of the (CGCC) monomer M, of a carboxyl group-containing compound selected from compounds having at least 3, more preferably at least 6, 8, 10, 15, 20, 25, ... carboxyl groups in their structure, in which at least 10 percent and at most 90 percent of the carboxyl groups are deprotonated (and therefore not containing Na, K, N, H4, Mg, Ca...), citric acid, isocitric acid; ethylenediaminetetraacetic acid; nitriloacetic acid; tartaric acid; oligomeric and polyacrylic acids; oligomeric and polymethacrylic acids; trimellitic acid; oligomeric amino acids having carboxy groups such as polyaspartic acid; oligomeric and polyglutamic acid; oligomeric and polyacetates having carboxy groups such as poly(glyoxylic)aldehyde; oxidized starch (amylopectin, amylose polyglucuronates; cellulose oxidized to celluronates; natural polycarboxylic polysaccharides such as xylans; pectinic acid; alginic acid; carboxymethylated polysaccharides based on 1,4-, 1,3-, and 1,6-polyglucans; polyuronic acids based on 1,4-, 1,3-, and 1,6-polyglucans; polygalacturones; carboxyl group-containing compounds, preferably selected from the group comprising carboxylated polysaccharides, more preferably carboxylated cellulose, and even more preferably carboxylated methylcellulose (carboxymethylcellulose, "CMC"); and c) at least one (non-carboxylated) sugar and/or polysaccharide, such as glucose, starch degradation products, maltodextrin, in an amount of 2 to 50% by weight, preferably 5 to 35% by weight, more preferably 10 to 30% by weight, and most preferably 15 to 25% by weight, based on the total weight of the (S) monomer M,
and d) at least one emulsifier selected from nonionic and anionic surfactants,
i) at least one nonionic surfactant,
anionic emulsifiers having at least one anionic group selected from phosphate, phosphonate, sulfate and sulfonate groups;
anionic emulsifiers, typically used in the form of their alkali metal salts, in particular their sodium salts, or in the form of their ammonium salts;
Preferably, anionic emulsifiers having at least one sulfate or sulfonate group or at least one phosphate or phosphonate group, more preferably having at least one sulfonate or sulfate group, most preferably having only one sulfonate or one sulfate group,
a) an anionic emulsifier having at least one sulfate or sulfonate group, preferably
salts of alkyl sulfates, in particular C8 to C22 alkyl sulfates, in particular alkali metal and ammonium salts,
the salts, in particular alkali metal and ammonium salts, of sulfuric acid monoesters of C2-C3 alkoxylated alkanols, in particular of sulfuric acid monoesters of C2-C3 alkoxylated C8-C22 alkanols, preferably having a C2-C3 alkoxylation level (AO level) ranging from 2 to 40;
- sulfuric acid monoesters of C2-C3 alkoxylated alkylphenols, in particular the salts of sulfuric acid monoesters of C2-C3 alkoxylated C4-C18-alkylphenols, in particular the alkali metal and ammonium salts (AO level preferably 3-40),
salts, especially alkali metal and ammonium salts, of alkylsulfonic acids, in particular C8-C22-alkylsulfonic acids,
dialkyl esters, in particular salts of di-C4 to C18-alkyl esters of sulfosuccinic acid, in particular alkali metal and ammonium salts,
- the salts, in particular the alkali metal and ammonium salts, of alkylbenzenesulfonic acids, in particular C4-C22 alkylbenzenesulfonic acids, and - the salts, in particular the alkali metal and ammonium salts, of mono- or disulfonated alkyl-substituted diphenyl ethers, for example bis(phenylsulfonic acid) ethers having a C4-C24 alkyl group on one or both aromatic rings;
(The term "C2-C3 alkoxylated" means that the compound is ethoxylated, propoxylated or coethoxylated/propoxylated, i.e., that the compound is obtained by a process that introduces polyethylene oxide, polypropylene oxide or poly(ethylene oxide-co-propylene oxide) groups, respectively.)
Selected from:
b) anionic emulsifiers having at least one phosphate or phosphonate group are preferably
salts, especially alkali metal and ammonium salts, of mono- and dialkyl phosphates, in particular C8-C22-alkyl phosphates,
- phosphoric acid monoesters of C2-C3-alkoxylated alkanols, preferably having an alkoxylation level in the range from 2 to 40, in particular in the range from 3 to 30, for example phosphoric acid monoesters of ethoxylated C8-C22 alkanols, preferably having an ethoxylation level (EO level) in the range from 2 to 40, phosphoric acid monoesters of propoxylated C8-C22 alkanols, preferably having a propoxylation level (PO level) in the range from 2 to 40, and salts, in particular alkali metal and ammonium salts, of phosphoric acid monoesters of ethoxylated-co-propoxylated C8-C22 alkanols, preferably having an ethoxylation level (EO level) in the range from 1 to 20 and a propoxylation level of 1 to 20,
salts of phosphoric acid monoesters of C2-C3-alkoxylated alkylphenols, in particular the salts of phosphoric acid monoesters of C2-C3-alkoxylated C4-C18-alkylphenols, in particular the alkali metal and ammonium salts (AO level preferably 3-40),
- the salts, in particular of C8-C22-alkylphosphonic acids, of which the alkali metal and ammonium salts are preferred, and - the salts, in particular of C4-C22-alkylbenzenephosphonic acids, of which the alkali metal and ammonium salts are preferred;
More preferred anionic emulsifiers are those from the following group:
salts of alkyl sulfates, in particular C8 to C22 alkyl sulfates, in particular alkali metal and ammonium salts,
salts, especially alkali metal salts, of sulfuric acid monoesters of C2-C3-alkoxylated alkanols, in particular of sulfuric acid monoesters of C2-C3-alkoxylated C8-C22-alkanols, preferably having an AO level in the range from 2 to 40;
sulfuric acid monoesters of C2-C3-alkoxylated alkylphenols, in particular those of C2-C3-alkoxylated C4-C18-alkylphenols (AO level preferably 3-40),
alkylbenzenesulfonic acids, in particular C4-C22 alkylbenzenesulfonic acids, and for example mono- or disulfonated alkyl-substituted diphenyl ethers of bis(phenylsulfonic acid) ethers having a C4-C24 alkyl group on one or both aromatic rings;
ii) at least one nonionic surfactant,
for example,
C2-C3-alkoxylated mono-, di- and trialkylphenols, in which the number of repeating units of the alkylene oxide derived moiety is preferably from 3 to 50 and/or the alkyl groups are preferably C4-C10-alkyl;
- C2-C3 alkyloxates of long-chain alcohols, such as ethoxylates, propoxylates or ethoxylate-co-propoxylates, in which the number of repeating units of the alkylene oxide-derived moiety is preferably between 3 and 100 and/or the alkyl group is preferably C8-C36-alkyl, and - polyethylene oxide/polypropylene oxide homo- and copolymers, which may comprise alkylene oxide units copolymerized in random distribution or in the form of blocks or mixtures of homoblocks and random blocks,
More preferably, emulsifiers selected from aromatic aliphatic or aliphatic nonionic emulsifiers selected from those having alkyl groups C8-C30 with an average alkoxylation level of 5 to 100, particularly preferably those having linear C12-C20 alkyl groups and an average alkoxylation level of 10 to 50, C2-C3-alkoxylated monoalkylphenols, and C2-C3-alkoxylated long-chain alkanols;
and e) optionally sulfate ions, and f) optionally sulfite ions, wherein preferably the amount of M1 is 80 to 99.99 mol %, more preferably the amount of M1 is at least 98%, the amount of M2 is 0.01 to 20 mol %, more preferably 0.1, even more preferably 0.2, even more preferably 0.5, most preferably 0.7, preferably at most 10, even more preferably at most 5, more preferably at most 2%, most preferably the amount of M1 is about 99 wt %, the amount of M2 is about 1 wt %, and the total amount of M1+M2 is 100 wt %, and wherein the dispersion has, after completion of the polymerization, a pH of at most 4, more preferably less than 4, even more preferably at most 3.8, even more preferably at most 3.6, more preferably at least 2.5, even more preferably at least 3, even more preferably at least 3.2, most preferably at least 3.4.

Embodiment 2:
(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; and (M2) at least one (meth)acrylic acid ester is (meth)acrylic acid, which is linked via an ether function to a polyalkylene oxide derived block (PAO), the PAO consisting of 20 to 30 alkylene oxide (AO), most preferably 25 AO units, the PAO preferably being linked via the ether function to a C14 to C22-aliphatic alkanol, most preferably 2. The dispersion of claim 1, wherein (M3) is not present, and wherein (M4) is further bonded to a C16/18-aliphatic alkanol, and AO is selected from EO and PO and/or BuO, more preferably EO and PO, and EO is in an amount of from 75% by weight, more preferably at least 90% by weight, and most preferably essentially EO only, based on the total AO; and further comprises methacrylic acid, wherein the methacrylic acid ester and free methacrylic acid are in a ratio of about 70% by weight/30% to 80% by weight/20% by weight, more preferably about 75% by weight/25% by weight.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Embodiment 22:
22. The use according to any one of embodiments 19 to 21 for imparting opacity.

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

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

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

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

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

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

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

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

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

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

The following examples will further illustrate the present invention without limiting its scope.

NTU value: Please refer to the table measured with liquid detergent.

General description of the implementation example

General Process Description: 1. Heat precharge under nitrogen at 120 uppm to 60/70°C internal temperature. 2. Add 5% Feed 1 in 1 minute and hold at temperature for 5 minutes. 3. Start Feed 2 (4 hours 15 minutes) and Feed 3 (4 hours 15 minutes). 4. 15 minutes after starting Feed 2 and Feed 3, start remaining Feed 1 (3 hours 30 minutes).
5. At the end of Feed 2 and Feed 3, add Feed 4 (1 minute) and hold for 5 minutes. 6. Start Feed 5 (1 hour 30 minutes). 7. Hold for 30 minutes after Feed 5, then add Feed 6 (1 minute). 8. Hold for 30 minutes. 9. Cool to an internal temperature of 23°C. 10. Test with a 125 μm filter while the filter is loaded.

Equipment - 4L cylindrical glass reactor - V4A round anchor stirrer - Gravimetric feed module - Heating bath

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

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

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

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

pH measurement: Pour the dispersion into a 250 ml beaker and measure the pH at 25°C using a Knick Portamess pH electrode (combined electrode). The measurement is carried out for 15 seconds until a constant pH value is reached.

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

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

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

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

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

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

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

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

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

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

D6 (JP 59155411 A, Nippon Synthetic Chemical Industry, JP 1983-028686 A) describes a copolymer of an oxyalkylene group-containing unsaturated monomer and vinyl acetate in solution polymerization in alcohol. The copolymerization of vinyl acetate includes an oxyalkylene group-containing unsaturated monomer (such as methacrylic acid). The number of oxyalkylene groups, i.e., n, is advantageously 1 to 50, preferably about 3 to 50. The oxoalkylene group may terminate with an alkyl. A preferred example is allylpolyoxoethylene, with one example being (10EO)-oxoethylene methacrylate. The modified vinyl acetate resin 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, among other applications. No biodegradation results have been published. The use of polycarboxylates such as carboxymethyl cellulose to improve biodegradability is not disclosed.

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

A terpolymer consisting of vinyl alcohol, vinyl acetate, and alkylpolyoxoethylene methacrylate ester is claimed in D8 (EP 199358 to Celanese Corp). The fabric protector comprises at least 50% vinyl alcohol in the terpolymer. The terpolymer is used as a barrier layer in a thermoplastic process for packaging articles. No biodegradation results have been published. The use of polycarboxylates such as carboxymethyl cellulose to improve biodegradability is not disclosed.

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

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

As a result of these trends, there is a strong need for new biodegradable cleaning additives that provide at least equivalent cleaning properties and a reduced CO2 footprint by being bio-based, biodegradable, or even both. The materials should preferably exhibit good primary cleaning activity, soil removal against oily/greasy and particulate stains, and/or improve whiteness retention, thus also minimizing the amount of suspended and emulsified oily/greasy and particulate stains that redeposit on fabrics or hard surfaces, etc.

It was therefore an object to provide an opacifier for compositions such as detergent, cleaning and/or fabric and home care compositions/formulations that has improved biodegradability.

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

The aqueous dispersions of the present invention, obtainable or obtained by the process according to the present invention, can be used as opacifiers in certain compositions, such as detergent, cleaning and/or fabric and home care compositions/formulations.

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

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

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

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

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

Similarly, the terms "substantially free of..." or "substantially free from..." or "essentially (containing/comprising)..." may be used herein; this means that the indicated material is at the very minimum not intentionally added to form part of the composition, or preferably is not present at analytically detectable levels. It is meant to encompass compositions in which the indicated material is present only as an impurity in one of the other intentionally included materials. The indicated material may be present, if at all, at levels of less than 1%, or even less than 0.1%, or even less than 0.01%, or even 0% by weight of the composition.

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

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

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

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

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

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

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

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

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

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

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

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

pH measurements are performed as described in the experimental section.

Throughout this specification, the term "compound of the present invention" may be used in place of "(aqueous) dispersion of the present invention" and "(aqueous) dispersion of this (present) invention" to mean that the compound is disclosed herein as the present invention, is defined by its structure and/or its manufacturing process, and/or can be obtained by the process defined herein.

The definitions and preferences given in the "Definitions" section above are included as part of the present invention, as described herein below.

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

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

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

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

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

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

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

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

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

CGCC is believed to be able to interact with polymerized moieties derived from at least one monomer M2 within the polymer product dispersed in the dispersion. Such interactions appear to provide superior compatibility and stability to the dispersion; they also favor attacks on the chemical structure, thus resulting in the observed high biodegradation rates of the aqueous polymer dispersions, which are higher than those of dispersions that do not contain the carboxyl-containing compound (CGCC).

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

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

In preferred variations of the above two embodiments, (S) is a maltodextrin having a DE value of 10 to 30, preferably 12 to 16 or 25 to 30.

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

Such degraded starches can be obtained by known means, such as chemical degradation, catalytic degradation using a suitable catalyst or enzymes. In this specification, (S) is preferably derived from enzymatic degradation, as this is a clean and rapid approach that essentially does not involve chemical residues from the degradation reaction in the degradation products (other than starch and sugars derived from starch).

Furthermore, the use of maltodextrin provides increased stability at lower storage temperatures for the dispersions of the present invention.

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

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

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

As a result of the polymerization reaction, the aqueous dispersion may contain sulfites and/or sulfates, primarily resulting from the use of persulfate initiators.

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

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

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

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

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

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

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

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

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

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

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

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

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

Another subject of the present invention is therefore a cleaning composition, fabric care and home care product, preferably a laundry cleaning composition, laundry treatment product or laundry care product or laundry cleaning product, preferably a liquid laundry detergent formulation or liquid laundry detergent product, comprising at least one aqueous polymer dispersion as detailed herein above and/or an aqueous polymer dispersion obtainable from the process as detailed herein above, wherein such composition or product exhibits improved opacity.

Such compositions or products of the present invention include at least one aqueous polymer dispersion as detailed hereinabove and/or an aqueous polymer dispersion obtainable from the process detailed hereinabove, such polymer dispersions having polymer structures similar to those described hereinabove in all of their embodiments, variants, and preferred, more preferred, etc. embodiments, as detailed hereinabove.

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

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

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

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.

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

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

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

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

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

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

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

The selection of additional surfactants and further cleaning adjuncts in these embodiments can depend on the application and desired benefits.

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

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

Compositions and formulations for industrial and institutional cleaning include those designed to clean any type of soiled material or surface, such as hard surface cleaners for any type of surface, including tiles, carpets, PVC surfaces, wooden surfaces, metal surfaces, lacquered surfaces, etc.

The cleaning composition comprises a surfactant system in an amount sufficient to impart 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% surfactant system by weight of the composition. In further embodiments, the cleaning composition comprises from about 5% to about 30% surfactant system by weight of the composition. The surfactant system may include a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, and combinations thereof. Those skilled in the art will understand that a detersive surfactant includes any surfactant or surfactant mixture that aids in the cleaning, stain removal, or laundering of soiled materials.

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

Such cleaning compositions, their components, their general composition, and more specific compositions are all known and are shown, for example, in publications 800542 and 800500 published by Protegas, Liechtenstein, and in WO 2022/136409 and WO 2022/136408. The opacifying compounds, if actually used or merely intended to be used therein, can be partially or completely replaced by the aqueous polymer dispersions of the present invention; if not utilized, the aqueous polymer dispersions of the present invention can be added in the amounts indicated herein. These aforementioned documents also disclose various types of formulations for cleaning compositions, and all types of such compositions are equally applicable to the cleaning compositions contemplated herein.

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

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

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

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

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

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

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

The composition can be enclosed in a single- or multi-compartment pouch. A multi-compartment pouch can have at least two, at least three, or at least four compartments. A multi-compartment pouch includes compartments that are side-by-side and/or nested. The composition contained in the pouch or its compartments can be a liquid, a solid (such as a powder), or a combination thereof.

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

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

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

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

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

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

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

Suitable examples of such cleaning adjuvants and their amounts of use are described, for example, in WO 99/05242, U.S. Pat. Nos. 5,576,282, 6,306,812 B1, and 6,326,348 B1.

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

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

In addition to the surfactant system and graft polymer, the liquid cleaning composition may additionally comprise, and preferably comprises at least one of, a rheology control/adjusting agent, an emollient, a moisturizer, a skin rejuvenation active, and a solvent.

The solid composition may additionally contain, and preferably contains at least one of, a filler, a bleaching agent, a bleach activator, and a catalytic material.

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

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

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

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

The cleaning compositions of the present invention may comprise, in addition to all other ingredients mentioned, one or more enzymes, more preferably a protease and/or amylase, selected from those disclosed hereinabove; even more preferably, the protease is a protease having at least 90% sequence identity to SEQ ID NO: 22 of EP 1921147 B1 and having the amino acid substitution R101E (according to BPN' numbering), and the amylase is an amylase having at least 90% sequence identity to SEQ ID NO: 54 of WO 2021032881 A1; such enzymes are preferably present in the formulation at a level of from about 0.00001% to about 5% by weight of enzyme protein, preferably from about 0.00001% to about 2% by weight, more preferably from about 0.0001% to about 1% by weight, or even more preferably from about 0.001% to about 0.5% by weight, based on the weight of the composition.

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

(In all weight percentages below; if the ingredient is added as a solution or dispersion, the percentage refers to the active substance content, i.e., typically the solids content of the ingredient in such solution or dispersion.)

The liquid laundry detergent according to the present invention comprises:
0.05 to 5% of at least one aqueous polymer dispersion (% by solids);
0.05 to 10% of at least one cleaning polymer;
1 to 50% surfactant;
0.1 to 40% of a builder, cobuilder and/or chelating agent;
0.1 to 50% of other adjuvants;
It is made up of water to make up 100%.

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

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

The liquid hand dish detergent according to the present invention comprises:
0.05 to 5% of at least one dispersion of the present invention;
1 to 50% surfactant;
0.1 to 50% of other adjuvants;
It is made up of water to make up 100%.

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

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

In all three tables above: * (60% by weight of vinyl acetate grafted onto polyethylene glycol with an Mn of 6,000 g/mol as the graft substrate (based on the total weight of the polymer; produced according to the general disclosure of WO 2007138054 A1))

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

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

Most Preferred Embodiment
Claim 1
below,
a) an ethylenically unsaturated monomer M,
(1) (M1) at least one vinyl ester, preferably comprising vinyl acetate, more preferably comprising at least 50%, even more preferably at least 90%, of vinyl acetate; and (2) (M2) at least one (meth)acrylic acid ester, optionally comprising as a minor component methacrylic acid, wherein the (meth)acrylic acid in the methacrylic acid ester is linked via an ether functional group to a polyalkylene oxide derived block (PAO), the PAO consisting of 2 to 40 alkylene oxide (AO), most preferably 25 AO-units, the PAO preferably comprising C1 to C24, preferably at least C4, alkylene oxides via the ether functional group. more preferably further bonded to at least a C6, even more preferably a C8-C24-aliphatic alkanol, most preferably a C18-aliphatic alkanol, wherein AO is preferably selected from EO, PO and/or BuO, more preferably at least EO in an amount of from 50 wt. %, more preferably at least 75 wt. %, even more preferably at least 90 wt. %, most preferably essentially EO only, based on total AO; preferably comprising methacrylic acid, more preferably methacrylic acid ester and free methacrylic acid in a ratio of about 70 wt. %/30 wt. %-80 wt. %/20 wt. %, more preferably about 75 wt. %/25 wt. %;
(3) (M3) Optional further monomers (preferably absent) that are polymerizable with M1 and M2.
an ethylenically unsaturated monomer M comprising:
b) 1 to 15 wt. %, preferably 2 to 10 wt. %, more preferably 3 to 8 wt. %, and most preferably 4 to 6 wt. %, based on the total weight of the (CGCC) monomer M, of a carboxyl group-containing compound selected from compounds having at least 3, more preferably at least 6, 8, 10, 15, 20, 25, ... carboxyl groups in their structure, in which at least 10 percent and at most 90 percent of the carboxyl groups are deprotonated (and therefore not containing Na, K, N, H4, Mg, Ca...), citric acid, isocitric acid; ethylenediaminetetraacetic acid; nitriloacetic acid; tartaric acid; oligomeric and polyacrylic acids; oligomeric and polymethacrylic acids; trimellitic acid; oligomeric amino acids having carboxy groups such as polyaspartic acid; oligomeric and polyglutamic acid; oligomeric and polyacetates having carboxy groups such as poly(glyoxylic)aldehyde; oxidized starch (amylopectin, amylose polyglucuronates; cellulose oxidized to celluronates; natural polycarboxylic polysaccharides such as xylans; pectinic acid; alginic acid; carboxymethylated polysaccharides based on 1,4-, 1,3-, and 1,6-polyglucans; polyuronic acids based on 1,4-, 1,3-, and 1,6-polyglucans; polygalacturones; carboxyl group-containing compounds, preferably selected from the group comprising carboxylated polysaccharides, more preferably carboxylated cellulose, and even more preferably carboxylated methylcellulose (carboxymethylcellulose, "CMC"); and c) at least one (non-carboxylated) sugar and/or polysaccharide, such as glucose, starch degradation products, maltodextrin, in an amount of 2 to 50% by weight, preferably 5 to 35% by weight, more preferably 10 to 30% by weight, and most preferably 15 to 25% by weight, based on the total weight of the (S) monomer M,
and d) at least one emulsifier selected from nonionic and anionic surfactants,
i) at least one nonionic surfactant,
anionic emulsifiers having at least one anionic group selected from phosphate, phosphonate, sulfate and sulfonate groups;
anionic emulsifiers, typically used in the form of their alkali metal salts, in particular their sodium salts, or in the form of their ammonium salts;
Preferably, anionic emulsifiers having at least one sulfate or sulfonate group or at least one phosphate or phosphonate group, more preferably having at least one sulfonate or sulfate group, most preferably having only one sulfonate or one sulfate group,
a) an anionic emulsifier having at least one sulfate or sulfonate group, preferably
salts of alkyl sulfates, in particular C8 to C22 alkyl sulfates, in particular alkali metal and ammonium salts,
the salts, in particular alkali metal and ammonium salts, of sulfuric acid monoesters of C2-C3 alkoxylated alkanols, in particular of sulfuric acid monoesters of C2-C3 alkoxylated C8-C22 alkanols, preferably having a C2-C3 alkoxylation level (AO level) ranging from 2 to 40;
- sulfuric acid monoesters of C2-C3 alkoxylated alkylphenols, in particular the salts of sulfuric acid monoesters of C2-C3 alkoxylated C4-C18-alkylphenols, in particular the alkali metal and ammonium salts (AO level preferably 3-40),
salts, especially alkali metal and ammonium salts, of alkylsulfonic acids, in particular C8-C22-alkylsulfonic acids,
dialkyl esters, in particular salts of di-C4 to C18-alkyl esters of sulfosuccinic acid, in particular alkali metal and ammonium salts,
- the salts, in particular the alkali metal and ammonium salts, of alkylbenzenesulfonic acids, in particular C4-C22 alkylbenzenesulfonic acids, and - the salts, in particular the alkali metal and ammonium salts, of mono- or disulfonated alkyl-substituted diphenyl ethers, for example bis(phenylsulfonic acid) ethers having a C4-C24 alkyl group on one or both aromatic rings;
(The term "C2-C3 alkoxylated" means that the compound is ethoxylated, propoxylated or coethoxylated/propoxylated, i.e., that the compound is obtained by a process that introduces polyethylene oxide, polypropylene oxide or poly(ethylene oxide-co-propylene oxide) groups, respectively.)
Selected from:
b) anionic emulsifiers having at least one phosphate or phosphonate group are preferably
salts, especially alkali metal and ammonium salts, of mono- and dialkyl phosphates, in particular C8-C22-alkyl phosphates,
- phosphoric acid monoesters of C2-C3-alkoxylated alkanols, preferably having an alkoxylation level in the range from 2 to 40, in particular in the range from 3 to 30, for example phosphoric acid monoesters of ethoxylated C8-C22 alkanols, preferably having an ethoxylation level (EO level) in the range from 2 to 40, phosphoric acid monoesters of propoxylated C8-C22 alkanols, preferably having a propoxylation level (PO level) in the range from 2 to 40, and salts, in particular alkali metal and ammonium salts, of phosphoric acid monoesters of ethoxylated-co-propoxylated C8-C22 alkanols, preferably having an ethoxylation level (EO level) in the range from 1 to 20 and a propoxylation level of 1 to 20,
salts of phosphoric acid monoesters of C2-C3-alkoxylated alkylphenols, in particular the salts of phosphoric acid monoesters of C2-C3-alkoxylated C4-C18-alkylphenols, in particular the alkali metal and ammonium salts (AO level preferably 3-40),
- the salts, in particular of C8-C22-alkylphosphonic acids, of which the alkali metal and ammonium salts are preferred, and - the salts, in particular of C4-C22-alkylbenzenephosphonic acids, of which the alkali metal and ammonium salts are preferred;
More preferred anionic emulsifiers are those from the following group:
salts of alkyl sulfates, in particular C8 to C22 alkyl sulfates, in particular alkali metal and ammonium salts,
salts, especially alkali metal salts, of sulfuric acid monoesters of C2-C3-alkoxylated alkanols, in particular of sulfuric acid monoesters of C2-C3-alkoxylated C8-C22-alkanols, preferably having an AO level in the range from 2 to 40;
sulfuric acid monoesters of C2-C3-alkoxylated alkylphenols, in particular those of C2-C3-alkoxylated C4-C18-alkylphenols (AO level preferably 3-40),
alkylbenzenesulfonic acids, in particular C4-C22 alkylbenzenesulfonic acids, and for example mono- or disulfonated alkyl-substituted diphenyl ethers of bis(phenylsulfonic acid) ethers having a C4-C24 alkyl group on one or both aromatic rings;
ii) at least one nonionic surfactant,
for example,
C2-C3-alkoxylated mono-, di- and trialkylphenols, in which the number of repeating units of the alkylene oxide derived moiety is preferably from 3 to 50 and/or the alkyl groups are preferably C4-C10-alkyl;
- C2-C3 alkyloxates of long-chain alcohols, such as ethoxylates, propoxylates or ethoxylate-co-propoxylates, in which the number of repeating units of the alkylene oxide-derived moiety is preferably between 3 and 100 and/or the alkyl group is preferably C8-C36-alkyl, and - polyethylene oxide/polypropylene oxide homo- and copolymers, which may comprise alkylene oxide units copolymerized in random distribution or in the form of blocks or mixtures of homoblocks and random blocks,
More preferably, emulsifiers selected from aromatic aliphatic or aliphatic nonionic emulsifiers selected from those having alkyl groups C8-C30 with an average alkoxylation level of 5 to 100, particularly preferably those having linear C12-C20 alkyl groups and an average alkoxylation level of 10 to 50, C2-C3-alkoxylated monoalkylphenols, and C2-C3-alkoxylated long-chain alkanols;
and e) optionally sulfate ions, and f) optionally sulfite ions, wherein preferably the amount of M1 is 80 to 99.99 mol %, more preferably the amount of M1 is at least 98%, the amount of M2 is 0.001 to 20 mol %, more preferably 0.1, even more preferably 0.2, even more preferably 0.5, most preferably 0.7, preferably at most 10, even more preferably at most 5, more preferably at most 2%, most preferably the amount of M1 is about 99 wt %, the amount of M2 is about 1 wt %, and the total amount of M1+M2 is 100 wt %, and wherein the dispersion has, after completion of the polymerization, a pH of at most 4, more preferably less than 4, even more preferably at most 3.8, even more preferably at most 3.6, more preferably at least 2.5, even more preferably at least 3, even more preferably at least 3.2, most preferably at least 3.4.

Embodiment 2:
(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; and (M2) at least one (meth)acrylic acid ester is (meth)acrylic acid, which is linked via an ether function to a polyalkylene oxide derived block (PAO), the PAO consisting of 20 to 30 alkylene oxide (AO), most preferably 25 AO units, the PAO preferably being linked via the ether function to a C14 to C22-aliphatic alkanol, most preferably 2. The dispersion of claim 1, wherein (M3) is not present, and wherein (M4) is further bonded to a C16/18-aliphatic alkanol, and AO is selected from EO and PO and/or BuO, more preferably EO and PO, and EO is in an amount of from 75% by weight, more preferably at least 90% by weight, and most preferably essentially EO only, based on the total AO; and further comprises methacrylic acid, wherein the methacrylic acid ester and free methacrylic acid are in a ratio of about 70% by weight/30% to 80% by weight/20% by weight, more preferably about 75% by weight/25% by weight.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Embodiment 22:
22. The use according to any one of embodiments 19 to 21 for imparting opacity.

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

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

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

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

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

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

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

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

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

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

The following examples will further illustrate the present invention without limiting its scope.

NTU value: Please refer to the table measured with liquid detergent.

General description of the implementation example

General Process Description: 1. Heat precharge under nitrogen at 120 uppm to 60/70°C internal temperature. 2. Add 5% Feed 1 in 1 minute and hold at temperature for 5 minutes. 3. Start Feed 2 (4 hours 15 minutes) and Feed 3 (4 hours 15 minutes). 4. 15 minutes after starting Feed 2 and Feed 3, start remaining Feed 1 (3 hours 30 minutes).
5. At the end of Feed 2 and Feed 3, add Feed 4 (1 minute) and hold for 5 minutes. 6. Start Feed 5 (1 hour 30 minutes). 7. Hold for 30 minutes after Feed 5, then add Feed 6 (1 minute). 8. Hold for 30 minutes. 9. Cool to an internal temperature of 23°C. 10. Test with a 125 μm filter while the filter is loaded.

Equipment - 4L cylindrical glass reactor - V4A round anchor stirrer - Gravimetric feed module - Heating bath

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

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

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

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

pH measurement: Pour the dispersion into a 250 ml beaker and measure the pH at 25°C using a Knick Portamess pH electrode (combined electrode). The measurement is carried out for 15 seconds until a constant pH value is reached.

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

Claims (15)

below,
a) an ethylenically unsaturated monomer M,
(1) (M1) at least one vinyl ester, preferably comprising vinyl acetate, more preferably comprising at least 50% vinyl acetate, and (2) (M2) at least one (meth)acrylic acid ester, optionally comprising as a minor component methacrylic acid, wherein the (meth)acrylic acid in the methacrylic acid ester is linked via an ether functionality to a polyalkylene oxide derived block (PAO), the PAO consisting of 2 to 40 alkylene oxide (AO), most preferably 25 AO-units, the PAO preferably comprising a C1 to C24, preferably at least C4, more preferably at least C6, even more preferably C8 to C24-aliphatic alkanoate, via the ether functionality. alkane, most preferably a C18-aliphatic alkanol, wherein the AO is preferably selected from EO, PO and/or BuO, more preferably at least EO is present in an amount of from 50% by weight, more preferably at least 75% by weight, even more preferably at least 90% by weight, most preferably essentially EO only, based on the total AO; preferably comprising methacrylic acid, more preferably the methacrylic acid ester and free methacrylic acid are in a ratio of about 70% by weight/30% to 80% by weight/20% by weight, more preferably about 75% by weight/25% by weight;
(3) (M3) Optional further monomers (preferably absent) that are polymerizable with M1 and M2.
an ethylenically unsaturated monomer M comprising:
b) 1 to 15% by weight, preferably 2 to 10% by weight, based on the total weight of (CGCC) monomers M, of carboxyl group-containing compounds selected from compounds having at least three carboxyl groups in their structure, in which at least 10 percent and at most 90 percent of the carboxyl groups are deprotonated, such as citric acid, isocitric acid; ethylenediaminetetraacetic acid; nitriloacetic acid; tartaric acid; oligomeric and polyacrylic acids; oligomeric and polymethacrylic acids; trimellitic acid; oligomeric amino acids having carboxy groups, such as polyaspartic acid; oligomeric and polyglutamic acid; oligomeric and polyacetates having carboxy groups, such as poly(glyoxylic)aldehyde; oxidized starch (azathioprine); carboxylated oligomeric and polymeric sugars such as carboxylated celluloses (mixtures of cellulose, mylopectin, and amylose); polyglucuronates; cellulose oxidized to celluronate; natural polycarboxylic polysaccharides such as xylans; pectinic acid; alginic acid; carboxymethylated polysaccharides based on 1,4-, 1,3-, and 1,6-polyglucans; polyuronic acids based on 1,4-, 1,3-, and 1,6-polyglucans; polygalacturons; carboxyl group-containing compounds, preferably selected from the group comprising carboxylated polysaccharides, more preferably carboxylated celluloses, and even more preferably carboxylated methylcellulose (carboxymethylcellulose, "CMC"); and c) at least one non-carboxylated sugar and/or polysaccharide, such as glucose, starch degradation products, or maltodextrin, in an amount of 2 to 50% by weight, preferably 5 to 35% by weight, based on the total weight of the (S) monomer M,
and d) at least one emulsifier selected from nonionic and anionic surfactants;
e) optionally sulfate ions, and f) optionally sulfite ions,
Preferably, the amount of M1 is 80 to 99.99 mol %, the amount of M2 is 0.01 to 20 mol %, preferably at most 10, even more preferably at most 5, more preferably at most 2%, the total amount of M1+M2 is 100 wt %, and said dispersion has a pH of at most 4 after completion of said polymerization. (M1) the vinyl ester monomer comprises at least 50%, and even more preferably at least 90%, vinyl acetate, based on the total molar amount of vinyl esters; and (M2) the at least one (meth)acrylic acid ester is (meth)acrylic acid linked via an ether functional group to a polyalkylene oxide derived block (PAO), the PAO consisting of 20 to 30 alkylene oxide (AO), most preferably 25 AO units, the PAO preferably further linked via an ether functional group to a C14 to C22-aliphatic alkanol, most preferably a C16/18-aliphatic alkanol, the AO being selected from EO and PO and/or BuO, more preferably EO and PO, the EO being in an amount of from 75% by weight, more preferably at least 90% by weight, most preferably essentially EO only, based on the total AO; and further comprising methacrylic acid, the methacrylic acid ester and the free methacrylic acid being in a ratio of about 70% by weight/30% to 80% by weight/20% by weight, more preferably about 75% by weight/25% by weight, and The dispersion of claim 1 , wherein (M3) is not included. 3. The dispersion of claim 2, wherein (M1) the vinyl ester monomer comprises at least 90% vinyl acetate, preferably essentially vinyl acetate, based on the total molar amount of vinyl esters, and (M2) the at least one (meth)acrylic acid ester is (meth)acrylic acid linked via ether functionality to a polyalkylene oxide derived block (PAO), the PAO consisting of 23 to 27 alkylene oxide (AO), most preferably an average of 25 AO-units, the PAO preferably further linked via ether functionality to an essentially C16/18-aliphatic alkanol, most preferably a C16/18-aliphatic alkanol, the AO being essentially EO; and further comprising methacrylic acid, the methacrylic acid ester and the free methacrylic acid being in a ratio of about 70%/30% to 80%/20% by weight, more preferably about 75%/25% by weight. 4. The dispersion of claim 3, wherein (M1) is vinyl acetate, and (M2) the at least one (meth)acrylic acid ester is methacrylic acid bonded to a polyethylene oxide block (PEO) via an ether functional group, the PEO consisting of an average of 25 AO units, the PEO further bonded to a C16/18-aliphatic alkanol via an ether functional group, and further comprising methacrylic acid, the methacrylic acid ester and the free methacrylic acid being in a ratio of about 75%/25% by weight. The dispersion of any one of claims 1 to 4, wherein the (CGCC) is a carboxyl group-containing compound selected from carboxylated polysaccharides, more preferably carboxylated celluloses, and even more preferably carboxylated methylcellulose (carboxymethylcellulose, "CMC"), in an amount of preferably 2.5 to 10 wt%, most preferably about 5 wt%, based on the total amount of monomers (M1+M2+M3). The dispersion according to any one of claims 1 to 5, wherein the dispersed polymer particles have a D[4,3] value determined by static light scattering from at least 400 and up to 1000 nm. The dispersion according to any one of claims 1 to 6, wherein (S) the at least one saccharide and/or polysaccharide is a starch degradation product, preferably maltodextrin, in an amount of 10 to 30% by weight, preferably 15 to 25% by weight, and more preferably 17 to 23% by weight, based on the total weight of the monomer M. The dispersion of claim 7, wherein (S) is a degraded starch having a dextrose equivalent according to Lane and Eynon in the range of 2 to 40%. The dispersion according to any one of claims 1 to 8, wherein compound S is a degraded starch having a number average molecular weight in the range of 300 to 2000 daltons as determined by osmometry, each in a weight percent based on the total weight of the monomers (M1 + M2 + M3) preferably in the range of 5 to 150, more preferably up to 70, even more preferably up to 50, more preferably from 10, even more preferably from 15, and most preferably from 20. A method for producing a polymer dispersion according to any one of claims 1 to 9, comprising:
A) an ethylenically unsaturated monomer M,
(1) (M1) at least one vinyl ester, preferably comprising vinyl acetate, more preferably comprising at least 50%, even more preferably at least 90%, of vinyl acetate; and (2) (M2) at least one (meth)acrylic acid ester, optionally comprising as a minor component methacrylic acid, wherein the (meth)acrylic acid in the methacrylic acid ester is linked via an ether functional group to a polyalkylene oxide derived block (PAO), the PAO consisting of 2 to 40 alkylene oxide (AO), most preferably 25 AO-units, the PAO preferably comprising a C1 to C24, preferably at least C4, more preferably at least C6, even more preferably C8 to C24-aliphatic alkanoate, via the ether functional group. alkane, most preferably a C18-aliphatic alkanol, wherein the AO is preferably selected from EO, PO and/or BuO, more preferably at least EO is present in an amount of from 50% by weight, more preferably at least 75% by weight, even more preferably at least 90% by weight, most preferably essentially EO only, based on the total AO; preferably comprising methacrylic acid, more preferably the methacrylic acid ester and free methacrylic acid are in a ratio of about 70% by weight/30% to 80% by weight/20% by weight, more preferably about 75% by weight/25% by weight;
(3) (M3) Optional further monomers (preferably absent) that are polymerizable with M1 and M2.
an ethylenically unsaturated monomer M comprising:
at least one emulsifier,
- water,
- 1 to 15% by weight, preferably 2 to 10% by weight, more preferably 3 to 8% by weight, most preferably 4 to 6% by weight, based on the total weight of the (CGCC) monomers M, of carboxyl group-containing compounds selected from compounds having at least 3, more preferably at least 6, 8, 10, 15, 20, 25 or more carboxyl groups in their structure, in which at least 10 percent and at most 90 percent of the carboxyl groups are deprotonated and therefore form salts with counterions selected from Na, K, NH4, Mg, Ca, and from citric acid, isocitric acid; ethylenediaminetetraacetic acid; nitriloacetic acid; tartaric acid; oligomeric and polyacrylic acids; oligomeric and polymethacrylic acids; trimellitic acid; oligomeric amino acids containing carboxy groups, such as polyaspartic acid; oligomeric and polyglutamic acid; poly Carboxylated oligomers and polyacetates such as (glyoxylic) aldehyde; carboxylated oligomeric and polymeric sugars such as oxidized starches, e.g., amylopectin, a mixture of amylose; polyglucronates; cellulose oxidized to celluronate; natural polycarboxylic polysaccharides such as xylans; pectinic acid; alginic acid; carboxymethylated polysaccharides based on 1,4-, 1,3-, and 1,6-polyglucans; polyuronic acids based on 1,4-, 1,3-, and 1,6-polyglucans; polygalacturons; carboxyl-containing compounds, preferably selected from the group comprising carboxylated polysaccharides, more preferably carboxylated cellulose, and even more preferably carboxylated methylcellulose (carboxymethylcellulose, "CMC"); and (S) in the presence of at least one non-carboxylated sugar and/or polysaccharide, such as glucose, starch degradation products, maltodextrin, in an amount of 2 to 50% by weight, preferably 5 to 35% by weight, more preferably 10 to 30% by weight, most preferably 15 to 25% by weight, based on the total weight of the monomer M,
polymerizing using at least one radical initiator, or preferably a peroxide and a reducing compound, more preferably a radical initiator pair comprising at least one persulfate and ascorbic acid and/or isoascorbic acid as radical polymerization initiators;
Such polymerization is
- in a reaction vessel equipped with either a pressure device and/or a device for controlling the boiling of the components, by which means the components can be contained in the reaction vessel during reaction at high temperature;
at a temperature of 60 to 90, preferably 70 to 80°C;
- carried out at a pH of at most 4, more preferably below 4, even more preferably at most 3.8, even more preferably at most 3.6;
and B) optionally adding additional radical initiator or initiator couple to further reduce the content of unreacted monomer and/or reduce the color of the resulting polymer dispersion;
C) optionally adding at least one additional reducing compound to reduce the color of the resulting polymer dispersion;
D) optionally adding at least one further additive that may be required or desired as an additional component into the resulting polymer dispersion;
E) optionally carrying out a step of removing volatilizable compounds from the reaction mixture by using a distillation step and/or a stripping step using steam or gas, preferably steam;
F) optionally filtering the polymer dispersion from the previous step, preferably using a 125 micrometer filter;
wherein the polymer dispersion is obtained. The method of claim 10, wherein the radical polymerization initiator additionally contains a transition metal. The method according to any one of claims 10 to 11, wherein at least one hydroperoxide and at least one sulfite salt are used in the post-polymerization step. The method of claim 12, wherein at least 5% of the total amount of hydroperoxide added is added after the addition of the sulfite is completed. Use of an aqueous polymer dispersion according to claims 1 to 9 or an aqueous polymer dispersion obtainable or obtained by the method according to any one of claims 10 to 13 as an opacifying component, preferably in liquid and semi-liquid compositions in the field of cleaning compositions for use on fabrics and hard surfaces, for use in industrial and institutional cleaning, wherein
said at least one aqueous polymer dispersion is present in a concentration of from about 0.01% to about 10% by weight (based on the solids content of the aqueous polymer dispersion) based on the total weight of such composition or product;
Preferably, the composition meets the following requirements:
a. preferably comprising at least one enzyme selected from one or more lipases, hydrolases, amylases, proteases, cellulases, mannanases, hemicellulases, phospholipases, esterases, xylanases, DNases, dispersins, pectinases, oxidoreductases, cutinases, lactases, and peroxidases, more preferably at least two of said species, and if an enzyme is included, preferably also comprising at least one enzyme stabilizing system;
b. comprising from about 1% to about 70% by weight of a surfactant system;
c) comprising an effective amount of at least one additional cleaning adjunct, and d) exhibiting improved cleaning 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 according to any one of claims 10 to 14 in an amount of 0.01 to 10% (based on the solids content of said aqueous polymer dispersion), based on the total solids content of such formulation,
Optionally, a) to c)
a. at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, mannanases, hemicellulases, phospholipases, esterases, xylanases, DNases, dispersins, pectinases, oxidoreductases, cutinases, lactases, and peroxidases, more preferably at least two of said species (if an enzyme is included, preferably also at least one enzyme stabilizing system);
b. about 1% to about 70% by weight of a surfactant system;
c. further comprising an effective amount of at least one additional cleaning adjunct;
Preferably it is a cleaning composition or a fabric and home care product, more preferably a cleaning composition, more preferably a laundry detergent or a dishwashing detergent;
Even more preferably it is a concentrated liquid detergent formulation, a single dose laundry detergent formulation, a liquid hand dishwashing detergent formulation, most preferably a liquid laundry detergent formulation or a liquid hand dishwashing detergent formulation;
optionally further comprising at least one antimicrobial agent, preferably 2-phenoxyethanol, in an amount of from 2 ppm to 5%, more preferably from 0.1 to 2%, by weight of the composition;
Optionally, a liquid or semi-liquid formulation comprising 4,4'-dichloro 2-hydroxydiphenyl ether at a concentration of 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6%, each based on the weight of the composition.