Biodegradable Graft Polymers

Abstract

The present invention relates to novel graft polymers comprising a copolymer backbone (A) as graft substrate having polymer side chains (B) grafted thereon. The polymer side chains (B) are obtainable by polymerization of at least one vinyl ester monomer (B1) and optionally further monomers (B2), and - if present - the weight ratio of monomer (B2) to monomer (B1) is less than 0.5. The copolymer backbone (A) is obtainable by polymerization of at least two monomers selected from the group ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide, the distribution of the alkylene oxide moieties within the copolymer backbone is in random order and the molecular weight M of the copolymer backbone is in the range of 0.5 to 1.5. n (g / mol) is in the range of 500-7000. Further claimed is a process for obtaining such graft polymers, preferably carried out by free radical polymerization. Also claimed is the use of such graft polymers, for example in fabric care and home care products, as well as fabric care and home care products comprising such graft polymers.

Description

[Technical field]

[0001] The present invention relates to novel graft polymers comprising a copolymer backbone (A) as graft substrate having polymer side chains (B) grafted thereon. The polymer side chains (B) are obtainable by polymerization of at least one vinyl ester monomer (B1) and optionally further monomers (B2), and - if present - the weight ratio of monomer (B2) to monomer (B1) is less than 0.5. The copolymer backbone (A) is obtainable by polymerization of at least two monomers selected from the group ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide, the distribution of the alkylene oxide moieties within the copolymer backbone is in random order and the molecular weight M of the copolymer backbone is in the range of 0.5 to 1.5. n (g / mol) is in the range of 500 to 7000. The invention further relates to a process for obtaining such grafted polymers, preferably carried out by free radical polymerization. The invention further relates to the use of such grafted polymers, for example in fabric care and home care products. Another subject of the invention is the fabric care and home care products themselves, which contain such grafted polymers. [Background technology]

[0002] Efforts have already been made in various countries to ban microplastics, especially in cosmetics. Beyond the ban of these insoluble microplastics, there is an intense exchange of ideas regarding future requirements for soluble polymers used in consumer products. It is therefore highly desirable to identify new, more biodegradable ingredients for such applications. This problem is mostly severe for polymers produced by radical polymerization that are primarily based on carbon-only backbones (backbones that do not contain heteroatoms such as oxygen), since carbon-only backbones are particularly difficult for microorganisms to degrade. Even radically produced graft polymers with industrially important polyethylene glycol backbones show only limited biodegradation in wastewater. However, the polymers described according to the present invention are preferably produced by radical graft polymerization and have improved biodegradability compared to the prior art.

[0003] WO 2007 / 138053 discloses amphiphilic graft polymers based on a water-soluble polyalkylene oxide (A) as graft substrate and side chains formed by polymerizing a vinyl ester component (B), said polymers having an average of less than one graft site per 50 alkylene oxide units and an average molar mass M of 3000 to 100000. However, WO 2007 / 138053 does not contain any disclosure regarding the biodegradability of the respective graft polymers disclosed therein; only a "water-soluble polyalkylene oxide" is specified as the backbone.

[0004] WO 03 / 042262 relates to a graft polymer comprising (A) a polymeric graft backbone containing no monoethylenically unsaturated units and (B) polymeric side chains formed from a copolymer of two different monoethylenically unsaturated monomers (B1) and (B2), each containing a nitrogen-containing heterocycle, the proportion of the amount of side chains (B) being 35-55% by weight of the total polymer. However, the graft polymer according to WO 03 / 042262 is not based on a vinyl ester monomer in each of the polymeric side chains grafted onto the backbone. Besides, WO 03 / 042262 does not disclose the biodegradability of the graft polymers disclosed therein.

[0005] US Patent No. 5,318,719A relates to a new class of biodegradable water-soluble graft copolymers with building properties, anti-filming properties, dispersibility and threshold crystal inhibiting properties, comprising (a) an acid functional monomer and, optionally, (b) other water-soluble monoethylenically unsaturated monomers copolymerizable with (a), grafted to a biodegradable substrate comprising a polyalkylene oxide and / or a polyalkoxylated material. However, US Patent No. A5,318,719 requires that each side chain of the graft polymer contains a large amount of an acid functional monomer, such as acrylic acid or methacrylic acid. Such acid monomers are not useful in the context of the present invention.

[0006] US 2019 / 0390142 relates to fabric care compositions comprising a graft copolymer, which may be composed of: (a) a polyalkylene oxide, such as polyethylene oxide (PEG); (b) N-vinylpyrrolidone (VP); and (c) a vinyl ester, such as vinyl acetate. However, US 2019 / 0390142 does not disclose any of the currently required backbones or biodegradability; all examples disclose only polyethylene oxide as the backbone.

[0007] Unpublished patent application PCT / EP2021 / 053446 relates to a graft polymer comprising a block copolymer backbone (A) as a graft substrate having polymer side chains (B) grafted thereon. The polymer side chains (B) are obtainable by polymerization of at least one vinyl ester monomer (B1) and optionally N-vinylpyrrolidone as optional further monomer (B2). Most preferably, the block copolymer backbone (A) is a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG). However, the backbone currently required is not disclosed.

[0008] WO 2020 / 005476 discloses a fabric care composition comprising a graft copolymer and a so-called processing aid, the graft copolymer comprising a polyalkylene oxide as a backbone based on ethylene oxide, propylene oxide or butylene oxide, preferably polyethylene oxide, and N-vinylpyrrolidone and vinyl esters as side chains grafted to the backbone, with monomers in both the backbone and in a specific ratio, however only polyethylene oxide as the backbone is explicitly disclosed.

[0009] WO 2020 / 264077 discloses cleaning compositions containing a combination of enzymes and polymers, such compositions being suitable for removing stains from soiled materials. The publication discloses so-called "suspension graft copolymers" selected from the group consisting of poly(vinyl acetate)-g-poly(ethylene glycol), poly(vinylpyrrolidone)-poly(vinyl acetate)-g-poly(ethylene glycol), and combinations thereof. However, a backbone is not required in the present invention.

[0010] WO 0018375 discloses a pharmaceutical composition comprising a graft polymer obtained by polymerizing at least one vinyl ester of an aliphatic C1-C24 carboxylic acid in the presence of a polyether, the vinyl ester being preferably vinyl acetate. In the most preferred version, the graft polymer is prepared from grafting vinyl acetate onto a PEG of Mw 6000 g / mol and subsequent hydrolysis of the vinyl acetate to alcohol (which then resembles the polymer obtained from the hypothetical monomer "vinyl alcohol"). The main application is the formation of coatings and films on solid pharmaceutical dosage forms such as tablets.

[0011] WO 0018375 discloses polyethers with number average molecular weights in the range of less than 500000 g / mol, preferably in the range of 300-100000 g / mol, particularly preferably in the range of 500-20000 g / mol, very particularly preferably in the range of 800-15000 g / mol, as polymer backbone. It is further stated that it is advantageous to use homopolymers of ethylene oxide or copolymers with an ethylene oxide content of 40-99% by weight, thus a content of ethylene oxide units in the ethylene oxide polymers preferably used of 40-100 mol %. Suitable comonomers for these copolymers are said to be propylene oxide, butylene oxide and / or isobutylene oxide, suitable examples being copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide, copolymers of ethylene oxide, propylene oxide and at least one butylene oxide. The ethylene oxide content in the copolymer is stated to be preferably between 40 and 99 mol %, the propylene oxide content between 1 and 60 mol % and the butylene oxide content in the copolymer between 1 and 30 mol %. Linear as well as branched homo- or copolymers are said to be usable as graft substrates for grafting.

[0012] However, WO 0018375 only exemplifies "polyethylene glycol / polypropylene glycol block copolymers" PEG 6000 and 9000 (having an average molecular weight of about 8000), and "polyglycerol" (having an average molecular weight of 2200) (all in g / mol). Five examples use only vinyl acetate, and only one uses vinyl acetate and methyl methacrylate as monomers. No other monomers are exemplified. All examples employ hydrolysis of the polymerized vinyl acetate monomer as a final step.

[0013] Thus, WO 0018375 does not produce or characterize polymers containing unhydrolyzed vinyl acetate as claimed in the present invention.

[0014] Additionally, WO 0018375 does not disclose or claim any specific graft polymers made from polyalkylene oxide polymers other than PEG as the polymer backbone.

[0015] The disclosure itself focuses on a different composition comprising only PEG grafted with vinyl acetate and then hydrolyzed to vinyl alcohol for use as a film-forming polymer in pharmaceutical applications.

[0016] Also, WO 0018375 does not disclose the use of polymers as disclosed herein in detergent and cleaning or fabric care applications, and the disclosure is completely silent about such applications or uses. Summary of the Invention [Problem to be solved by the invention]

[0017] The object of the present invention is to provide novel grafted polymers which, when used in compositions such as cleaning compositions, should furthermore possess beneficial properties in terms of biodegradability and / or cleaning behavior. [Means for solving the problem]

[0018] The purpose of this is to (A) a copolymer backbone as a graft substrate, said copolymer backbone (A) being obtainable by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide, a. the distribution of alkylene oxide moieties within the copolymer backbone is in random order; b. A copolymer main chain having a molecular weight Mn (g / mol) in the range of 500 to 7000; (B) polymeric side chains grafted onto the copolymer backbone, said polymeric side chains (B) being obtainable by polymerization of at least one vinyl ester monomer (B1) and optionally at least one other monomer (B2), and - if present - the weight ratio of monomer (B2) to monomer (B1) being less than 0.5, preferably less than 0.4, more preferably less than 0.3, even more preferably less than 0.2 and most preferably less than 0.1; A graft polymer comprising: In weight percent based on the total weight of the graft polymer, 25-85% of a copolymer backbone (A); 15-75% polymer side chains (B); This is achieved by a graft polymer comprising: DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] The grafted polymer according to the present invention can be used, for example, in cleaning compositions and / or fabric care and home care products.The grafted polymer provides such compositions or products with at least the same, preferably even improved, anti-redeposition and cleaning performance, for example, in terms of soil redeposition and stain removal, compared with the corresponding polymer or grafted polymer according to the prior art.In addition, the grafted polymer according to the present invention provides improved biodegradability when used in such compositions or products, for example, cleaning compositions and / or fabric care and home care products.

[0020] The grafted polymers with enhanced biodegradability according to the invention can be advantageously used in washing and cleaning compositions, where they aid in the removal of hydrophobic soils from textiles or hard surfaces by surfactants, thus improving the washing and cleaning performance of the formulations, and furthermore they allow the removed soils to be better dispersed in the washing or cleaning liquor and prevent their redeposition on the surface of the material to be washed or cleaned.

[0021] As used herein, the articles "a" and "an," when used in the claims, are understood to mean one or more of the claimed or described subject matter. As used herein, the terms "include(s)" and "including" are not intended to be limiting.

[0022] The compositions of the present disclosure can "comprise" the components of the present disclosure (i.e., contain other ingredients), "consist essentially of" (contains primarily or almost only the recited ingredients, with only minor amounts of other ingredients, primarily limited to impurities), or "consist of" (i.e., contains only the recited ingredients, and in addition may contain only impurities that are unavoidable in the technical circumstances, and preferably contains only the recited ingredients).

[0023] Similarly, the terms "substantially free of..." or "substantially free from..." or "containing / comprising essentially no..." may be used herein; this means that the specified substance is, at a minimum, not intentionally added thereto to form part of the composition, or preferably is not present at analytically detectable levels. This is meant to encompass compositions in which the specified substance is present only as an impurity in one of the other intentionally included substances. The specified material may be present, if present at all, at a level of less than 1%, or even less than 0.1%, or even less than 0.01%, or even 0% by weight of the composition.

[0024] The term "about" as used herein, for example when written as "about X%", encompasses the exact numerical value "X" as well as small deviations of X, including deviations 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% from X (in this calculation, X is set to 100%) and smaller deviations. Needless to say, when the given numerical value X itself is already "100%" (e.g., purity), the term "about" can clearly mean deviations smaller than "100", and therefore only deviations smaller than "100".

[0025] The phrase "fabric care composition" is meant to include compositions and formulations designed for fabric treatment. 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-treatment agents, laundry auxiliaries, spray products, dry cleaning agents or compositions, laundry rinsing additives, washing additives, post-rinse fabric treatment agents, ironing aids, unit dose formulations, delayed delivery formulations, detergents contained on or within porous substrates or nonwoven sheets, and other suitable forms that may be obvious to those skilled in the art in light of the teachings herein and are detailed below when describing the 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 laundry operations, which are described in more detail below when describing the uses and applications of the grafted polymers of the present invention and compositions containing such grafted polymers.

[0026] Unless otherwise specified, all component or composition levels refer to the active portion of that component or composition and are exclusive of impurities, such as residual solvents or by-products that may be present in commercial sources of such component or composition.

[0027] All temperatures herein are in degrees Celsius (°C) unless otherwise specified. All measurements herein are made at atmospheric pressure at 20°C 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.

[0028] Graft Polymer The first subject of the invention is therefore (A) a copolymer backbone as a graft substrate, said copolymer backbone (A) being obtainable by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide, a. the distribution of alkylene oxide moieties within the copolymer backbone is in random order; b. a copolymer backbone having a molecular weight Mn (g / mol) in the range of 500 to 7000, preferably 6000 or less, more preferably 5000 or less, even more preferably 4500 or less, even more preferably 4000 or less, even more preferably 3500 or less, even more preferably 3000 or less, most preferably 2500, preferably at least 1000, more preferably at least 1200; (B) polymeric side chains grafted onto the copolymer backbone, said polymeric side chains (B) being obtainable by polymerization of at least one vinyl ester monomer (B1) and optionally at least one other monomer (B2), and - if present - the weight ratio of monomer (B2) to monomer (B1) being less than 0.5, preferably less than 0.4, more preferably less than 0.3, even more preferably less than 0.2 and most preferably less than 0.1; A graft polymer comprising: A copolymer main chain (A) in an amount of 25 to 85%, preferably 30 to 80%, more preferably 35 to 80%, even more preferably 40 to 75%, and most preferably 55 to 75% by weight based on the total weight of the graft polymer; and 15 to 75%, preferably 20 to 70%, more preferably 20 to 65%, even more preferably 25 to 60%, and most preferably 25 to 45% of the polymer side chain (B).

[0029] The ratio of the random copolymer backbone (A) to the polymer side chain (B) in the graft polymer exemplified in the present invention may not be limited to a specific value; in principle, any ratio known to those skilled in the art can be used. However, good results are obtained when the ratios as detailed above are used.

[0030] The copolymer backbone (A) itself is known to those skilled in the art, as are the processes for producing such a copolymer backbone, for example in EP 362688. Such processes are typically the copolymerization, using known means, of at least two alkylene oxides.

[0031] Thus, suitable copolymer backbones (A) having randomly arranged alkylene oxides for use within the present invention can be readily obtained by standard alkoxylation polymerization processes using the required alkylene oxides in the required ratios.

[0032] Regarding the copolymer backbone (A) of the graft polymer according to the invention, the copolymer backbone (A) is i) is obtainable by polymerization of at least two monomers selected from the group ethylene oxide, 1,2-propylene oxide or 1,2-butylene oxide, preferably at least ethylene oxide is selected as one of the monomers, more preferably ethylene oxide and propylene oxide are selected as the only monomers, and / or ii) It is preferred that the relative amount of EO in the polymer backbone A is in the range of 5-95%, preferably 10-90%, more preferably 15-85%, even more preferably at least 20-80% (all expressed as weight percent relative to the total mass of alkylene oxide in the polymer backbone (A)).

[0033] With regard to the graft polymer, furthermore, any of the previously defined preferences i) and ii) for the polymer backbone may be replaced by a third preference, namely It is preferable that this can be combined with iii) that essentially no monomer (B2) is used in the polymerization to obtain the side chain (B).

[0034] The graft polymers according to the invention preferably have a low polydispersity. Preferably, the graft polymers according to the invention and / or as detailed above have a polydispersity M of <5, preferably <3.5, more preferably <3, most preferably in the range of 1.0 to 2.5. w / M n (M w = weight average molecular weight, M n = number average molecular weight; polydispersity is unitless. g / mol / g / mol ]). M w and / or M n The respective values ​​of can be determined as described below in the experimental section.

[0035] The copolymer backbone (A) according to the invention and / or comprised within the graft polymer as detailed above may be end-capped or not end-capped (uncapped) at the respective end groups of the backbone. Thus, in the present invention, it is possible to optionally end-cap one or both end groups of the copolymer backbone (A), preferably the copolymer backbone (A) is not end-capped at both end groups or, if the copolymer backbone (A) is end-capped, the end-caps are C1-C 25 -Alkyl groups, preferably C1 to C4 groups.

[0036] In one particularly preferred embodiment of the present invention, the graft polymer of the present invention and / or as detailed above comprises (A) 55-75% by weight (relative to the total weight of the graft polymer) of a copolymer backbone (A) obtainable by polymerization of ethylene oxide and 1,2-propylene oxide as alkylene oxide monomers, the alkylene oxide monomer distribution in the backbone being in random order, the molecular weight Mn (g / mol) of the copolymer backbone being in the range of 1200-2500, and the relative amount of EO in the polymer backbone (A) being 20-80% (by weight relative to the total mass of alkylene oxides in the polymer backbone (A)); (B) 25-45% by weight (based on the total weight of the grafted polymer) of polymer side chains grafted onto the copolymer backbone derived from vinyl acetate as the only vinyl ester monomer (B1) with essentially no other monomers (B2) being used.

[0037] The copolymer (A) may contain various levels of hydrophilic ethylene glycol which affects the overall properties of the grafted polymer. The copolymer can be low, medium or high %EO, which affects the biodegradation properties as well as the performance in laundry formulations. Therefore, the relative amount of EO in the polymer backbone (A) is preferably between 20-80% (weight relative to the total mass of alkylene oxide in the polymer backbone (A)) to achieve good performance not only in application but also in biodegradation.

[0038] The polymer backbone may contain additional initiating blocks present when the process for preparing the polyalkylene oxide polymer begins. The initiating blocks react with alkylene oxides and the chains grow further to produce polyalkylene oxides containing the initiating blocks in the chain. Suitable initiating blocks are those that can react with alkylene oxides and have two hydroxyl groups, such as glycols, alkylene glycols, and diols; preferably, these initiating blocks are selected from glycerin, 2-methyl-1,3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, trismethylolpropane, water, pentaerythritol, sorbitol, saccharose, glucose, fructose, lactose, and similar compounds with similar chemical structures. In principle, diamines such as ethylenediamine, propylenediamine, diethylenetriamine, dipropylenetriamine, etc. are also possible, but these amines are not preferred in view of potential problems with respect to ecotoxicity upon biodegradation of the grafted polymers of the invention, especially if they are released again from the polymer structure.

[0039] In a more preferred embodiment, no such initiating blocks are used within the polymer backbone of the present invention.

[0040] With regard to the polymer side chains (B) contained in the graft polymer according to the invention, it is preferred that the polymer side chains (B) are obtained by radical polymerization and / or by the addition of at least one vinyl ester monomer (B1).

[0041] As vinyl ester monomer (B1) it is possible to use, besides vinyl acetate, vinyl propionate or vinyl laurate, any further vinyl esters known to the person skilled in the art, for example vinyl valerate, vinyl pivalate, vinyl neodecanoate, vinyl decanoate or vinyl benzoate.

[0042] If an optional further monomer (B2) is used to prepare the polymer side chains (B) in the graft polymer according to the invention, the ratio of the essential vinyl ester monomer (B1) to said further monomer (B2) can in principle be any value known to those skilled in the art. The amount of vinyl ester monomer (B1) is usually 1% by weight or more (with respect to the sum of (B1) and (B2)).

[0043] However, in a preferred embodiment, the graft polymer of the invention and / or as detailed above comprises polymeric side chains (B) which are obtained or obtainable by radical polymerization, in the presence of said polymeric backbone A, of at least one vinyl ester monomer (B1) and optionally at least one other monomer (B2), Preferably at least 10 wt.-% of the total weight of vinyl ester monomers (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably vinyl acetate and vinyl laurate, most preferably vinyl acetate, the remaining amount of vinyl esters may be any other known vinyl ester, preferably at least 60, more preferably at least 70, even more preferably at least 80, even more preferably at least 90 wt.-% of vinyl acetate, most preferably essentially only vinyl acetate (i.e. about 100 wt.-% or even 100 wt.-% of vinyl acetate) is used as vinyl ester (wt.-% based on the total weight of vinyl ester monomers B1 used), Preferably essentially no monomer (B2) is used.

[0044] In an even more preferred embodiment, the graft polymer of the present invention and / or as detailed above comprises (A) 55-75% by weight (relative to the total weight of the graft polymer) of a copolymer backbone (A) obtainable by polymerization of ethylene oxide and 1,2-propylene oxide as alkylene oxide monomers, the alkylene oxide monomer distribution in the backbone being in random order, the molecular weight Mn (g / mol) of the copolymer backbone being in the range of 1200-2500, and the relative amount of EO in the polymer backbone (A) being 20-80% (by weight relative to the total mass of alkylene oxides in the polymer backbone (A)); (B) 25-45% by weight (based on the total weight of the grafted polymer) of polymer side chains grafted onto the copolymer backbone, derived from vinyl acetate as the only vinyl ester monomer (B1), essentially without the use of monomer (B2).

[0045] The grafted polymer of the present invention may contain a certain amount of ungrafted polymers ("ungrafted side chains") formed from vinyl esters, e.g. polyvinyl acetate when only vinyl acetate is used, and / or homo- and copolymers of vinyl esters with other monomers when further monomers are used. The amount of such ungrafted vinyl acetate homo- and copolymers may be high or low depending on the reaction conditions, but is preferably reduced and therefore low. By this reduction, the amount of grafted side chains is preferably increased. Such reduction can be achieved by suitable reaction conditions, e.g. the input amount of vinyl ester and radical initiator and their relative amounts plus the amount of the main chain present. This is generally known to those skilled in the art.

[0046] The graft polymer of the present invention can be characterized by its degree of grafting (the number of sites where polymer side chains (B) are grafted onto the copolymer backbone (A)). The degree of grafting can be high or low depending on the reaction conditions. Preferably, the degree of grafting is low to medium, more preferably low. "Low" in this embodiment means that statistically there are less than 2 graft sites per 50 alkylene oxide units.

[0047] Adjustments to the degree of grafting and the amount of ungrafted polymer can be made to optimize performance in a particular area of ​​interest, such as desired performance in a particular (e.g., detergent) formulation, application area, or cleaning.

[0048] In another - but not preferred - embodiment of the invention, the polymeric side chain (B) of the graft polymer according to the invention is completely or - more preferably - at least partially hydrolyzed after the graft polymer itself has been obtained, which means that the complete or at least partial hydrolysis of the polymeric side chain (B) of the graft polymer is carried out after the polymerization process of the polymeric side chain (B) is completed.

[0049] By complete or at least partial hydrolysis of the polymer side chain (B) of the graft polymer according to the invention, each side chain unit originating from at least one vinyl ester monomer (B1) is converted from the respective ester functionality to an alcohol functionality in the polymer side chain (B). It should be noted that the corresponding vinyl alcohol is not suitable for use as a monomer in the polymerization process of the polymer side chain (B) from the standpoint of stability. To obtain an alcohol functionality (hydroxyl substituent) in the polymer side chain (B) of the graft polymer according to the invention, the alcohol functionality is typically introduced by hydrolysis of the ester functionality of the side chain.

[0050] From a theoretical point of view, each ester functional group of the polymer side chain (B) can be replaced with an alcohol functional group (hydroxy group). In such a case, the polymer side chain is fully hydrolyzed ("saponified").

[0051] Hydrolysis can be carried out by any method known to those of skill in the art, for example, hydrolysis can be induced by the addition of a suitable base, such as sodium hydroxide or potassium hydroxide.

[0052] However, in this embodiment of the invention, it is preferred that the polymer side chains (B) are only partially hydrolyzed, for example up to about 20%, 40% or 60% by weight (based on the total weight of the polymer side chains). In this embodiment, it is even more preferred that the polymer side chains (B) are fully or partially hydrolyzed after polymerization, preferably up to about 50% based on the amount of the at least one vinyl ester monomer (B1) used in the polymerization.

[0053] However, in the most preferred embodiment of the invention, the polymer side chains (B) are not hydrolyzed after polymerization.

[0054] In the graft polymers of the present invention and / or as detailed above, it is preferred that no other monomers are used in the respective polymerization process to obtain the polymeric side chain (B) other than those as defined above in relation to at least one vinyl ester monomer (B1) and the optional additional monomer (B2). However, if any further polymeric monomers are present other than the monomer according to (B1) and optionally (B2), such monomers (other than B1 and B2) are present in an amount of less than 1% of the total amount of monomers used to obtain the polymeric side chain (B). Preferably, the amount of said additional monomers is less than 0.5% by weight, even more preferably less than 0.01% by weight, and most preferably no additional monomers other than the monomers (B1) and optionally (B2) are present at all.

[0055] In further preferred embodiments thereof, the weight ratio of monomer (B2) to monomer (B1) is less than 0.5, preferably less than 0.4, more preferably less than 0.3, even more preferably less than 0.2, most preferably less than 0.1; and even more preferably, monomer (B2) is present in an amount of less than 1% of the total amount of monomers used to obtain the polymer side chain (B). Even more preferably, the amount of monomer (B2) is less than 0.5% by weight, even more preferably less than 0.01% by weight, and most preferably, there is essentially no monomer (B2) other than monomer (B1).

[0056] The monomer (B2) is in principle a monomer that is polymerizable with the vinyl ester monomer (B1). In the present invention, it is particularly preferred that no monomers containing acid functionality are used. In particular, the monomers used to obtain the polymer side chains (B) of the graft polymer according to the invention do not include any acid-functional monomers such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, vinyl-acetic acid or acryloxy-propionic acid.

[0057] The polymers of the present invention have at least one, and preferably two or more of the following properties, so that they can be successfully used in the various applications targeted by the present invention: a) A particular level of biodegradability, such that the biodegradability of the grafted polymer is at least 30, preferably at least 35, even more preferably at least 40%, within 28 days when tested according to OECD 301F (see also experimental section for measurement method). b) Some degree of water solubility of the polymer, so that the polymer can be used in the aqueous environments typically present in the fields of application generally targeted by the present invention. Preferably, the polymer of the present invention should exhibit moderate to good solubility, more preferably very good solubility, in the aqueous formulation environments typically used in such fields for various formulations, such as dishwashing, automatic dishwashing, hard surface cleaning, fabric washing, fabric care, cosmetic formulations, etc. c) The viscosity of the polymer solution must be such that it can be handled and provided to the user during and after production, optionally with a suitably high solid polymer concentration; this can be, for example, a "pure" (then normally liquid) product dissolved in a solvent, typically an aqueous solution comprising water and an organic solvent, water alone, or organic solvent alone, the viscosity of such polymer or polymer solution being in a range that allows the usual technological process steps, such as pouring, pumping, dosing, etc. Thus, the viscosity should preferably be in the range of less than about 4000 mPas, more preferably up to 3500 mPas, more preferably up to 3000 mPas, such as up to 4500, 3750, 3250, 2750 or even up to 2600 or lower, such as 2500, 2000, 1750, 1500, 1250, 1000, 750, 500, 250, 200, 150 or 100 mPas, with a polymer content (based on the total solids content of the polymer in the solution, which is defined as the weight percent of the dry polymer contained in the total weight of the polymer solution) of preferably at least 10% by weight, more preferably at least 20, even more preferably at least 40% by weight, most preferably at least 50% by weight, such as at least 60, 70, 80 or even 90% by weight. Viscosity can be measured either at 25°C or at elevated temperatures, such as at a temperature of 50°C or even at 60°C. This allows the polymer solution to be properly handled on a commercial scale. Of course, depending on the amount of solvent added, it is clear that as the amount of solvent increases, the viscosity decreases and vice versa, and can therefore be adjusted as desired. It is also clear that the measured viscosity depends on the measurement temperature, e.g. the viscosity of a given polymer with a given solids content, e.g. 80 wt%, will be higher when measured at a lower temperature and lower when measured at a higher temperature. In a preferred embodiment, the solids content of the as-prepared polymer without added solvent is between 70 and 99 wt%, more preferably between 75 and 85 wt%.In a more preferred embodiment, the solids content of the as-prepared polymer without added solvent is between 70-99 wt%, more preferably between 75-95 wt%, and is less than 3000 mPas, more preferably less than 3250 mPas, or even below 2750, 2600, 2500, 2000, 1750, 1500, 1250, 1000, 750, 500, or even 250 mPas, measured at 60° C. The viscosity can be measured as generally known for such polymers, preferably as described in the experimental section below.

[0058] To achieve these requirements, the following guidelines can be given as to how to achieve these properties of the polymers of the present invention: Biodegradability is generally enhanced with at least one of the following conditions: Molecular weight M of the random copolymer main chain (A) n but lower compared to higher molecular weights; · A lower weight percentage of polymer side chains (monomer B) is grafted to the backbone compared to a higher weight percentage.

[0059] Of course, further criteria should be evaluated for the individual performance of a specific polymer, and therefore for each formulation of a specific application.Since the polymers of the present invention show a wide range of usefulness, a comprehensive overview cannot be given, but the present application and examples provide guidance on how to prepare and select useful polymers with desired properties and how to tailor the properties to the desired requirements.Of course, one such criterion used in the field of home care and especially fabric care is performance in washing, for example, subjecting a specific material with a stain of a specific substance to a prescribed washing procedure.

[0060] In the examples some guidelines are given for application in the area of ​​fabric cleaning, i.e. general fabric care.

[0061] Depending on the particular need for a polymer with a defined biodegradability, water solubility and viscosity (i.e., handleability), how such a polymer may be obtained will be guided by the general and specific teachings herein, but is not intended to be limited to the specific examples presented.

[0062] The performance of the grafted polymer is believed to be excellent when the cloud point is approximately the same as the temperature of application. As low temperature washing trends increase, grafted polymers with lower cloud points may be preferred for such applications. This is believed to be especially true for the rinse benefits.

[0063] process Another subject of the invention is a process for preparing the inventive graft polymers described above, in which at least one monomer (B1) and optionally further monomers (B2) are polymerized in the presence of at least one copolymer backbone (A) to obtain at least one graft polymer according to the invention.

[0064] It should be noted that the grafting process, in which a polymer backbone, such as a copolymer backbone, is grafted with polymer side chains, is itself known to those skilled in the art. Any process known to those skilled in the art in this regard can be employed in the present invention.

[0065] In the process of the invention, the polymeric side chains (B) are preferably obtained by radical polymerization.

[0066] The radical polymerization itself is also known to those skilled in the art. The skilled artisan also understands that the process of the present invention can be carried out in the presence of a radical-forming initiator (C) and / or at least one solvent (D). The skilled artisan also understands each of the components itself.

[0067] "Radical polymerization" as used in the context of the present invention includes free radical polymerization as well as its variants such as controlled radical polymerization. Suitable control mechanisms are RAFT, NMP or ATRP, each of which is known to those skilled in the art along with suitable control agents.

[0068] In a preferred embodiment, the process for producing a graft polymer as described in accordance with the present invention and / or as described above in detail, comprises polymerizing at least one vinyl ester monomer (B1) and optionally at least one further monomer (B2) in the presence of at least one copolymer backbone (A), a free radical-forming initiator (C) and, optionally, at most 50% by weight of at least one organic solvent (D), based on the sum of components (A), (B1), optionally (B2), (C) and (D), at an average polymerization temperature such that the decomposition half-life of the initiator (C) is between 40 and 500 minutes, in such a way that the proportion of unconverted graft monomer (B1) and optional monomer (B2) and initiator (C) in the reaction mixture is always maintained in a quantitative deficit with respect to the copolymer backbone (A).

[0069] The amount of ((free) radical-forming) initiator (C), based in each case on the polymer side chains (B), is preferably 0.1 to 5% by weight, in particular 0.3 to 3.5% by weight.

[0070] In the process according to the invention, preferably, the steady-state concentration of radicals present at the average polymerization temperature is substantially constant and the grafting monomers (B1) or (B2) are always present in the reaction mixture only in low concentrations (for example less than or equal to 5% by weight in total), which makes it possible to control the reaction and to prepare grafted polymers with the desired low polydispersity in a controlled manner.

[0071] However, to ensure safe temperature control - especially when starting the polymerization in large quantities and / or when large amounts of monomer are present from the start - it is wise and therefore preferable to use additional effective temperature control means. This can be done by external or internal cooling; such cooling can be by internal and / or external coolers such as heat exchangers and / or by using reflux condensers when operating at the boiling point of the solvent or solvent mixture.

[0072] Of course, the same procedure can be used in the preferred embodiment described above where the monomer is added over an extended period of time and therefore the monomer concentration in the reaction volume is always low over time.

[0073] However, under such conditions, temperature control is usually not a critical point since the temperature is also at least partially controlled by the progress of the polymerization reaction by controlling the radical concentration and the available amount of polymerizable monomer. Of course, depending on the scale of the polymerization reaction, if the scale becomes large enough and the volume to surface ratio of the polymerization mixture becomes very large, additional cooling as described above may be necessary in both variants, batch or bulk reactions where large amounts of monomer are present from the start, or semi-continuous or continuous polymerization reactions, typically always with low monomer concentrations.

[0074] However, this is commonly known to those skilled in the art of carrying out commercial scale polymerizations and can therefore be adapted to suit the needs.

[0075] The term "average polymerization temperature" is intended herein to mean that the process is substantially isothermal, although temperature fluctuations may occur due to the exothermic nature of the reaction, and are preferably maintained within a range of + / - 10°C, more preferably within a range of + / - 5°C.

[0076] According to the present invention, the decomposition half-life of the (radical-forming) initiator (C) at the average polymerization temperature must be 40 to 500 minutes, preferably 50 to 400 minutes, and more preferably 60 to 300 minutes.

[0077] According to the invention, the initiator (C) and the grafting monomers (B1) and / or (B2) are advantageously added in such a way that undecomposed initiator and grafting monomers (B1) and / or (B2) are present in the reaction mixture in a substantially constant low concentration. The proportion of undecomposed initiator in the reaction mixture as a whole is preferably ≦15% by weight, in particular ≦10% by weight, based on the total amount of initiator metered in during the monomer addition.

[0078] In a more preferred embodiment, the process comprises polymerizing at least one vinyl ester monomer (B1) and optionally at least one other monomer (B2) in the presence of at least one polymer backbone (A), a free radical-forming initiator (C) and, optionally, up to 50% by weight of at least one organic solvent (D), based on the sum of components (A), (B1), optional (B2) and (C), at an average polymerization temperature such that the decomposition half-life of the initiator (C) is between 40 and 500 minutes, in such a way that the proportion of unconverted grafting monomer (B1) and optional (B2) and initiator (C) in the reaction mixture is always kept quantitatively deficient with respect to the polymer backbone (A), preferably at least 10% by weight of the total weight of vinyl ester monomers (B1) being vinyl acetate, vinyl propionate and vinyl laurate, more preferably vinyl acetate and vinyl laurate, most preferably acetic acid. Preferably at least 60, more preferably at least 70, even more preferably at least 80, even more preferably at least 90% by weight of vinyl acetate, most preferably essentially only vinyl acetate (i.e. about 100% by weight or even 100% by weight of vinyl acetate) is used as vinyl ester (% by weight based on the total weight of vinyl ester monomers B1 used), and - if (B2) is present - the weight ratio of optional monomer (B2) to monomer (B1) is less than 0.5, preferably less than 0.4, more preferably less than 0.3, even more preferably less than 0.2, most preferably less than 0.1, and even more preferably monomer (B2) is present in an amount of less than 1% by weight of the total amount of monomers used to obtain the polymer side chain (B), more preferably less than 0.5%, even more preferably less than 0.01%.

[0079] In an even more preferred embodiment, essentially no monomers (B2) are used other than monomers (B1).

[0080] The average polymerization temperature is suitably in the range of 50 to 140°C, preferably in the range of 60 to 120°C, and more preferably in the range of 65 to 110°C.

[0081] Examples of suitable initiators (C) having a decomposition half-life of 20 to 500 minutes in the temperature range of 50 to 140° C. are shown below: - tert-C4~C 12 -Alkyl hydroperoxide and tert-(C9-C 12 -aralkyl) hydroperoxides, such as tert-butyl peracetate, tert-butyl monoperoxymaleate, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, tert-amyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneodecanoate, tert-butyl peroxybenzoate, tert-amyl peroxybenzoate, and di-tert-butyl diperoxyphthalate, 12 -acylated derivatives; - tert-C8~C 14 -Alkylene bisperoxides, such as di-O-C4-C of 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane and 1,3-di(2-neodecanoylperoxyisopropyl)benzene 12 -acylated derivatives; - Ji (C2~C 12-alkanoyl) and dibenzoyl peroxides, such as diacetyl peroxide, dipropionyl peroxide, disuccinic acid peroxide, dicapryloyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, di(4-methylbenzoyl) peroxide, di(4-chlorobenzoyl) peroxide and di(2,4-dichlorobenzoyl) peroxide; - Peroxy (C4~C 12 -alkyl)carbonates tert-C4-C5-alkyl, for example, peroxy(2-ethylhexyl)carbonate tert-amyl; - Peroxydicarbonate (C2-C 12 -alkyl), for example, di(n-butyl) peroxydicarbonate and di(2-ethylhexyl) peroxydicarbonate.

[0082] Depending on the average polymerization temperature, examples of particularly suitable initiators (C) are: - Average polymerization temperature 50~60℃: tert-Butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate, tert-amyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneodecanoate, 1,3-di(2-neodecanoylperoxyisopropyl)benzene, di(n-butyl) peroxydicarbonate, and di(2-ethylhexyl) peroxydicarbonate; - Average polymerization temperature 60~70℃: tert-Butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate and di(2,4-dichlorobenzoyl)peroxide; - Average polymerization temperature 70~80℃: tert-Butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-amyl peroxypivalate, dipropionyl peroxide, dicapryloyl peroxide, didecanoyl peroxide, dilauroyl peroxide, di(2,4-dichlorobenzoyl) peroxide and 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane; - Average polymerization temperature 80~90℃: tert-Butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, dipropionyl peroxide, dicapryloyl peroxide, didecanoyl peroxide, dilauroyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, dibenzoyl peroxide and di(4-methylbenzoyl) peroxide; - Average polymerization temperature 90~100℃: tert-Butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl monoperoxymaleate, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide and di(4-methylbenzoyl peroxide); - Average polymerization temperature 100~110℃: tert-Butyl monoperoxymaleate, tert-butyl peroxyisobutyrate and tert-amyl peroxy(2-ethylhexyl)carbonate; - Average polymerization temperature 110~120℃: tert-Butyl monoperoxymaleate, tert-butyl peroxy-3,5,5-trimethylhexanoate and tert-amyl peroxy(2-ethylhexyl)carbonate.

[0083] Preferred initiators (C) are tert-C4-C5-alkyl hydroperoxides O-C4-C 12 -acylated derivatives, particularly preferred are tert-butyl peroxypivalate and tert-butyl peroxy-2-ethylhexanoate.

[0084] Particularly advantageous polymerization conditions can be easily set by precisely adjusting the initiator (C) and the polymerization temperature. For example, the preferred average polymerization temperature when tert-butyl peroxypivalate is used is 60 to 80°C, and when tert-butyl peroxy-2-ethylhexanoate is used is 80 to 100°C.

[0085] The polymerization reaction of the present invention can be preferably carried out in the presence of a small amount of solvent (D), which can be an organic solvent and / or water. Of course, it is also possible to use mixtures of different solvents (D). It is preferable to use water-soluble or water-miscible solvents.

[0086] When the solvent (D) is used as a diluent, it is generally used in an amount of 1 to 40% by weight, preferably 1 to 35% by weight, more preferably 1.5 to 30% by weight, most preferably 2 to 25% by weight, based on the sum of the components (A), (B1), optionally (B2) and (C) in each case.

[0087] Examples of suitable solvents (D) include the following: - Monohydric alcohols, preferably aliphatic C1-C 16 -Alcohols, more preferably aliphatic C2-C 12 -alcohols, most preferably C2-C4-alcohols, such as ethanol, propanol, isopropanol, butanol, sec-butanol and tert-butanol; - Polyhydric alcohols, preferably C2-C 10 -diols, more preferably C2-C6-diols, most preferably C2-C4-alkylene glycols, such as ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol; - alkylene glycol ether, preferably alkylene glycol mono(C1-C 12-alkyl) ethers and alkylene glycol di(C1-C6-alkyl) ethers, more preferably alkylene glycol mono- and di(C1-C2-alkyl) ethers, most preferably alkylene glycol mono(C1-C2-alkyl) ethers, such as ethylene glycol monomethyl and -ethyl ethers and propylene glycol monomethyl and -ethyl ethers; - polyalkylene glycols, preferably poly(C2-C4-alkylene) glycols having 2 to 20 C2-C4-alkylene glycol units, more preferably polyethylene glycols having 2 to 20 ethylene glycol units and polypropylene glycols having 2 to 10 propylene glycol units, most preferably polyethylene glycols having 2 to 15 ethylene glycol units and polypropylene glycols having 2 to 4 propylene glycol units, such as diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol; - polyalkylene glycol monoethers, preferably poly(C2-C4-alkylene) glycol mono(C1-C 25 -alkyl) ethers, more preferably poly(C2-C4-alkylene) glycol mono(C1-C 20 -alkyl) ethers, most preferably poly(C2-C3-alkylene) glycol mono(C1-C2-alkylene) glycols having 3 to 20 alkylene glycol units; 16 -alkyl) ethers; - carboxylic acid esters, preferably C1-C8-alkyl esters of C1-C6-carboxylic acids, more preferably C1-C4-alkyl esters of C1-C3-carboxylic acids, most preferably C2-C4-alkyl esters of C2-C3-carboxylic acids, such as, for example, ethyl acetate and ethyl propionate; aliphatic ketones, preferably having 3 to 10 carbon atoms, such as acetone, methyl ethyl ketone, diethyl ketone and cyclohexanone; - cyclic ethers, in particular tetrahydrofuran; - Water.

[0088] The solvent (D) is advantageously a solvent that is also used when formulating the graft polymer of the invention (for example for washing and cleaning compositions) and which may therefore remain in the polymerization product.

[0089] Preferred examples of such solvents are polyethylene glycols having 2 to 15 ethylene glycol units, polypropylene glycols having 2 to 6 propylene glycol units, and in particular alkoxylation products of C6-C8-alcohols (alkylene glycol monoalkyl ethers and polyalkylene glycol monoalkyl ethers).

[0090] In this specification, highly branched C8-C 16 Particularly preferred are the alkoxylation products of -alcohols, which allow the formulation of polymer mixtures having a free flowing property at 40-70° C. and a very low polymer content at relatively low viscosities. Branching may be present in the alkyl chain of the alcohol and / or in the polyalkoxylate moiety (copolymerized with at least one propylene oxide, butylene oxide or isobutylene oxide unit). Particularly suitable examples of such alkoxylation products are 2-ethylhexanol or 2-propylheptanol alkoxylated with 1-15 mol ethylene oxide, C alkoxylated with 1-15 mol ethylene oxide and 1-3 mol propylene oxide. 13 / C 15 Oxo alcohol or C 12 / C 14 Or C 16 / C 18 The fatty alcohol 2-propylheptanol alkoxylated with 1 to 15 mol of ethylene oxide and 1 to 3 mol of propylene oxide is preferred.

[0091] In an alternative embodiment, the polymerization is carried out using a mixture of at least one organic solvent and water.

[0092] In a further alternative embodiment, the polymerization is carried out using water as solvent (D).

[0093] The radical initiator (C) is preferably used in the form of a highly concentrated solution in one of the abovementioned solvents. The concentration, of course, depends on the solubility of the radical initiator. This concentration is preferably as high as possible so that as little organic solvent as possible is introduced into the polymerization reaction. If water is used as a solvent for introducing the initiator because the initiator is water-soluble, the concentration is not critical in terms of the residual level of water.

[0094] In a preferred embodiment, the amount of water is low, preferably less than 5% by weight, more preferably less than 1%, based on the total solvent.

[0095] In the process according to the invention, the random copolymer backbone (A), the graft monomers (B1) and, if appropriate, (B2), the initiator (C) and, if appropriate, the solvent (D) are usually heated in a reactor to the selected average polymerization temperature.

[0096] According to the invention, the polymerization is carried out so that there is always an excess of polymer (random copolymer backbone (A) and formed graft polymer (B)) in the reactor. The quantitative ratio of polymer to non-grafted monomer and initiator is generally ≧10:1, preferably ≧15:1, more preferably ≧20:1.

[0097] The polymerization process according to the invention can in principle be carried out in various types of reactors.

[0098] The reactor used is preferably a stirred tank into which the whole or part of the random copolymer backbone (A) is initially charged together with, if appropriate, the graft monomer (B1) or (B2), the initiator (C) and a portion of the solvent (D), generally up to 15% by weight of the specific total amount, heated to the polymerization temperature, and the remaining amounts of (B), (C) and, if appropriate, (D) are metered in, preferably separately. (B), (C) and, if appropriate, the remaining amounts of (D) are metered in over a period of preferably ≥ 2 hours, more preferably ≥ 4 hours, most preferably ≥ 5 hours.

[0099] In a particularly preferred variant thereof, the substantially solvent-free process, the entire amount of the random copolymer backbone (A) is initially charged as a melt, and the grafting monomers (B1) and, if appropriate, (B2) and, in addition, the initiator (C), preferably present in the form of a 10-50% by weight solution in one of the solvents (D), are metered in, the temperature being controlled in such a way that the selected average polymerization temperature is maintained during the polymerization, in particular within the range of + / - 10°C, in particular within the range of + / - 5°C.

[0100] In a further particularly preferred variant, the low-solvent process, the procedure is as described above, except that the solvent (D) is metered in during the polymerization to limit the viscosity of the reaction mixture. It is also possible to start the metered addition of the solvent only at a later point in time once the polymerization has progressed, or to add it in small portions.

[0101] The polymerization can be effected at normal pressure or at reduced or elevated pressure. If at the selected pressure the boiling points of the monomers (B1) or (B2) or of the optional diluent (D) used are exceeded, the polymerization is carried out with reflux cooling.

[0102] A post-polymerization process step can be added after the main polymerization reaction. For this purpose, an additional amount of initiator (dissolved in a solvent) can be added over a period of more than 0.5 hours and typically up to 3 hours, preferably about 1-2 hours, more preferably about 1 hour (although the period also depends on the reactor size), and the radical initiator and the solvent for the initiator are typically and preferably the same as the solvent for the main polymerization reaction. Of course, a different radical initiator and / or a different solvent can also be used.

[0103] The temperature of the post-polymerization process step may be the same as that of the main polymerization reaction (preferred in the present invention) or may be increased, typically by about 5 to 40°C, preferably 10 to 20°C.

[0104] The main polymerization reaction can be allowed to proceed for a period of time between the post-polymerization and the main polymerization, after which the post-polymerization reaction can be started by commencing the addition of additional radical initiator.

[0105] In the case of solvents with atmospheric boiling points below about 110-120°C, such solvents can be partially or essentially completely removed - as a purification step - by high temperature or vacuum distillation or stripping with a gas such as steam or nitrogen, for example stripping with steam, all at normal pressure or under reduced pressure, preferably by vacuum distillation, while higher boiling solvents will usually remain in the resulting polymer product. When mercaptoethanol is used as a chain transfer regulator, steam distillation is the preferred purification step. Thus, high boiling solvents such as 1-methoxy-2-propanol, 1,2-propanediol, and tripropylene glycol must be used in such a way that the amount of radical initiator is minimized as much as possible by using the radical initiator in as high a concentration as possible, unless such solvents form part of the formulation in which the graft polymer will be used.

[0106] The grafted polymer of the present invention, i.e. the polymer solution resulting from the process, may also be subjected to a means of concentration or drying.

[0107] The resulting grafted polymer solution can be concentrated by removing a portion of the solvent to increase the solid polymer concentration. This can be achieved by carrying out a distillation process, such as high temperature or vacuum distillation, until a desired solid content is reached. Such a process can be combined with a purification step as disclosed above, in which case the resulting grafted polymer solution is purified by removing a desired amount of solvent to remove some or all of the volatile components, such as volatile solvents and / or unreacted volatile monomers.

[0108] After the main polymerization and / or optional post-polymerization steps and optional purification steps, the grafted polymer solution can be further concentrated or dried by subjecting it to a means for partial or complete removal of volatile materials, such as roller-drum drying, spray drying, vacuum drying or freeze drying, preferably, mainly for cost reasons, drying such as spray drying. Such drying processes can also be combined with agglomeration or granulation processes, such as drying by spray-agglomeration or fluidized bed dryers.

[0109] use In principle, the grafted polymers of the present invention can be used in any application replacing conventional grafted polymers having the same or very similar composition (in terms of the polymer backbone and the amount of grafted monomers, in particular the type and amount of grafted monomers are similar or equivalent). Such applications include, for example: Cosmetics, Personal Care: Such compositions and formulations include shampoos, lotions, gels, sprays, soaps, makeup powders, lipsticks, and hairsprays.

[0110] Technical applications: such compositions and formulations include use as dispersants in any kind of adhesives, non-aqueous and preferably aqueous liquid or solid formulations, any kind of dispersions where it is typically required to disperse a solid or liquid in another liquid or solid, such as in oil field applications or automotive applications.

[0111] Lacquer, Paint and Stain Formulations: Such compositions and formulations include non-aqueous and preferably aqueous lacquers as well as stains, paints and finishes.

[0112] Agricultural formulations: Such compositions and formulations include those that contain agrochemically active materials in a liquid or solid environment.

[0113] Perfume Formulations: Such compositions and formulations include those in which the perfume is dissolved or dispersed in a liquid or solid composition so as to be uniformly dispersed and / or to maintain its stability, e.g., to maintain its scent profile over time; also included are compositions which release the perfume over time, e.g., extended release or delayed release formulations.

[0114] Another subject of the present invention is therefore the use of the grafted polymers according to the invention and / or obtainable by the process as detailed above or as disclosed hereinbefore, in fabric care and home care products, in cosmetic and personal care formulations, as emulsion breakers for crude oil, in technical applications such as pigment dispersions for inkjet inks, in electroplating formulations, in cement-based compositions, in agrochemical formulations, for example as dispersants, crystal growth inhibitors and / or solubilizers, in lacquer and colorant formulations. and / or in cleaning compositions, preferably in agrochemical and cleaning compositions and fabric care and home care products, in particular in cleaning compositions, preferably laundry and / or dishwashing detergent formulations, more preferably liquid laundry and / or hand dishwashing detergent formulations, for improving the removal of oily and greasy soils, for removing solid soils such as clay, for preventing dark stains on fabric surfaces and / or as scale inhibitors, or in particular for use as dispersants, crystal growth inhibitors and / or solubilisers in agrochemical compositions.

[0115] Another subject of the present invention is therefore also cleaning compositions, fabric care and home care products, institutional and corporate cleaning products, cosmetics or personal care products, oil field formulations such as emulsion breakers for crude oil, pigment dispersions for inkjet inks and inks containing the grafted polymer, electroplating products, cement-based compositions, dispersants for lacquers or paints and agrochemical formulations, preferably laundry detergents, cleaning compositions and / or fabric care and home care products, comprising at least one grafted polymer as defined above or obtained or obtainable by a process according to the invention and / or as previously detailed.

[0116] Further subjects of the present invention are fabric care and home care products, cleaning compositions, institutional and corporate cleaning products, cosmetics or personal care products, oil field formulations such as emulsion breakers for crude oil, pigment dispersions for inks such as inkjet inks, electroplating products, cementitious compositions, lacquers, paints, agrochemical formulations, preferably laundry detergents, cleaning compositions and / or fabric care and home care products, each containing at least one grafted polymer of the present invention and / or as described above.

[0117] Laundry detergents, cleaning compositions and / or fabric and household care products as such are known to those skilled in the art. Any compositions, etc., related to the respective applications and known to those skilled in the art can be used in connection with the present invention.

[0118] In a preferred embodiment, it is a cleaning composition and / or fabric care and home care product and / or commercial and institutional cleaning product comprising at least one graft polymer as defined above.In particular, it is a cleaning composition, preferably a laundry detergent formulation and / or a hand dish detergent formulation, more preferably a liquid laundry detergent formulation and / or a hand dish detergent formulation, for example for improving the cleaning and anti-redeposition performance in terms of soil redeposition and stain removal, especially for stain removal such as grease-covered oily soils of sebum and food and / or clay particles, and preferably a cleaning composition, more preferably a laundry detergent formulation and / or a hand dish detergent formulation, most preferably a liquid laundry detergent formulation and / or a hand dish detergent formulation, for improving the cleaning / first wash of oily and greasy stain removal, more preferably for stain removal such as grease-covered oily soils of sebum and food oil and / or clay particles.

[0119] Specifically, the grafted polymers of the present invention aid in the removal of a variety of hydrophobic and hydrophilic soils from textiles or hard surfaces by surfactants, such as body soils, food and oil soils, particulate soils such as clay or carbon black, grass stains, cosmetics, motor oil, etc., thus improving the washing and cleaning performance of the formulation ("improved cleaning performance").

[0120] The grafted polymer of the present invention also disperses the removed soil better in the washing or cleaning solution and prevents it from being reattached to the surface of the material being washed or cleaned ("anti-reattachment performance"). In this specification, the removed soil includes all typical soils present during the washing process, such as body soils, food and oil soils, particulate soils such as clay or carbon black, grass soils, cosmetics, motor oil, etc. Such anti-reattachment effect can be observed on various fabric types, including cotton, polycotton, polyester, polyether / polyurea copolymers (Spandex™), etc. In addition, such anti-reattachment effect is also effective on fabrics that have used fabric enhancers or when fabric washing is performed in the presence of fabric enhancers or other laundry additives such as freshness beads or bleaching agents.

[0121] In one embodiment, also preferred in the present invention, the cleaning composition further comprises (besides the at least one grafted polymer as defined above) at least one enzyme, preferably selected from one or more of the following: lipases, hydrolases, amylases, proteases, cellulases, mannanases, hemicellulases, phospholipases, esterases, xylanases, deoxyribonucleases, dispersins, pectinases, oxidoreductases, cutinases, lactases, and peroxidases, more preferably at least two of the above mentioned types.

[0122] Another subject of the present invention is therefore cleaning compositions, such as fabric care and home care products and institutional and institutional (I&I) cleaning products, comprising at least one grafted polymer as defined above, in particular for improved cleaning and anti-redeposition performance as previously detailed.

[0123] At least one grafted polymer described herein is present in the cleaning compositions of the present invention in an amount ranging from about 0.01% to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1% to about 10%, and most preferably from about 0.5% to about 5%, based on the total weight of such composition or product, and such cleaning compositions may further comprise, and preferably further comprise, from about 1% to about 70% by weight of a surfactant system.

[0124] Preferably, such cleaning compositions of the present invention are fabric and home care products or institutional and institutional (I&I) cleaning products, preferably fabric and home care products, more preferably laundry detergents or hand dish detergents comprising at least one inventive polymer and optionally further comprising at least one surfactant or surfactant system to enhance soil removal, dispersion and / or emulsification, and / or modify and / or maintain the whiteness of treated surfaces.

[0125] Even more preferably, the cleaning compositions of the present invention comprise at least one grafted polymer of the present invention, and optionally further comprise at least one surfactant or surfactant system - all as detailed above - which show improved cleaning and anti-redeposition performance among laundry and hand dishwashing applications, and even more specifically aimed at improved cleaning and anti-redeposition performance in laundry applications, most preferably laundry detergents, which may further comprise at least one enzyme selected from the list consisting of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, as well as combinations of at least two of the above mentioned types of enzymes.

[0126] In one embodiment of the present invention, the grafted polymers of the present invention can be preferably used in laundry care for improved cleaning and anti-redeposition and / or further whiteness maintenance. In another preferred embodiment, the grafted polymers of the present invention can be used to reduce dark stains on fabrics (anti-darkening stains), preferably in laundry applications.

[0127] In one preferred embodiment, the cleaning composition of the present invention is a liquid or solid laundry detergent composition.

[0128] In another preferred embodiment, the cleaning composition of the present invention is a liquid or solid (e.g., powder or tablet / unit dose) detergent composition for hand or automatic dishwashing, preferably a liquid hand dishwashing detergent composition. Such compositions are known to those skilled in the art.

[0129] In other embodiments, the cleaning compositions of the present invention are hard surface cleaning compositions that can be used to clean a variety of surfaces, such as hardwood, tile, ceramic, plastic, leather, metal, glass, and the like.

[0130] In other embodiments, the cleaning compositions are designed for use in cosmetic, personal care and pet care compositions, such as shampoo compositions, personal washes, liquid or bar soaps, etc.

[0131] In one embodiment, the grafted polymer of the present invention can be utilized in a cleaning composition comprising a surfactant system comprising a C10-C15 alkyl benzene 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.

[0132] In a further embodiment, the grafted polymer of the present invention can be utilized in cleaning compositions such as any type of laundry detergents comprising a C8 to C18 linear or branched alkyl ether sulfate containing 1 to 5 ethoxy units as a surfactant base and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants or mixtures thereof.

[0133] In a further embodiment, the grafted polymer of the present invention can be utilized in cleaning compositions such as any type of laundry detergents that contain a C12-C18 alkyl ethoxylate surfactant containing 5-10 ethoxy units as the surfactant base and one or more additional surfactants selected from anionic, cationic, amphoteric, zwitterionic or other non-ionic surfactants or mixtures thereof.

[0134] In one embodiment of the present invention, the grafted polymer is a component of a cleaning composition, preferably a laundry or dishwashing formulation, more preferably a liquid laundry or hand dishwashing formulation, each further comprising at least one surfactant, preferably at least one anionic surfactant.

[0135] In a further embodiment, the present invention also encompasses a composition comprising the graft polymer described herein above, further comprising an antimicrobial agent as disclosed herein below, 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, 0.1 to 2% phenoxyethanol.

[0136] In a further embodiment, the present invention also encompasses a method of protecting an aqueous composition from microbial contamination or growth, such composition comprising a grafted polymer as described herein above, 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 being preferably 2-phenoxyethanol.

[0137] 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 laundry softener composition, each of which comprises a grafted polymer as described herein above, and each of which further comprises 4,4'-dichloro 2-hydroxydiphenyl ether, at a concentration of 0.001-3%, preferably 0.002-1%, more preferably 0.01-0.6%, by weight of the composition.

[0138] 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 with a liquid laundry detergent composition or a liquid hand dishwashing composition, even more preferably with a liquid laundry detergent composition or a liquid laundry softener composition, each of which comprises a grafted polymer as described herein above, and such composition further comprises 4,4'-dichloro 2-hydroxydiphenyl ether.

[0139] The selection of the additional surfactant in these embodiments may depend on the application and the desired effect.

[0140] Description of cleaning compositions, formulations, and their ingredients As used herein, the phrase "cleaning composition" includes compositions and formulations designed for cleaning soiled materials, including those designed to clean any type of soiled material or surface.

[0141] "Industrial and institutional cleaning" compositions include cleaning compositions designed for use in industrial and institutional cleaning, such as those for use in cleaning any type of soiled material or surface, such as hard surface cleaners for any type of surface including tiles, carpets, PVC surfaces, wood surfaces, metal surfaces, lacquered surfaces, etc.

[0142] "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 rinsing 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, light duty liquid detergent compositions, heavy duty liquid detergent compositions, detergent gels commonly used in laundry, bleaching compositions, laundry additives, fabric enhancing compositions, and other suitable forms that may be apparent to those skilled in the art in light of the teachings herein. Such compositions may be used as laundry pre-treatments, laundry post-treatments, or may be added during the rinse or wash cycle of a laundry operation, preferably during the wash cycle of a laundry or dishwashing operation. More preferably, such fabric care and home care compositions are laundry cleaning compositions, laundry care products, or laundry washing products, most preferably liquid laundry detergent formulations or liquid laundry detergent products.

[0143] The cleaning composition 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, pearlescent balls, agglomerates, tablets, granular compositions, sheets, lozenges, beads, fibrous articles, bars, flakes, or mixtures thereof; types delivered in single, two, or multi-compartment pouches or containers; single-phase or multi-phase unit doses; spray or foam cleaners; wet wipes (i.e., cleaning compositions combined with nonwoven materials, such as those described in U.S. Pat. No. 6,121,165 by Mackey, et al.); dry wipes that are activated by the user or consumer by wetting with water (i.e., cleaning compositions combined with nonwoven materials, such as those described in U.S. Pat. No. 5,980,931 by Fowler, et al.); and other homogeneous, heterogeneous, or single-phase or multi-phase cleaning products.

[0144] The composition can be enclosed in a single compartment or a multi-compartment pouch. A multi-compartment pouch can have at least two, at least three, or at least four compartments. A multi-compartment pouch can include side-by-side and / or stacked compartments. The composition contained in the pouch or its compartments can be a liquid, a solid (such as a powder), or a combination thereof.

[0145] Non-limiting examples of "liquids" / "liquid compositions" include light duty and heavy duty liquid detergent compositions, fabric enhancers, detergent gels commonly used in laundry, bleaches and laundry additives. Gases, such as suspended bubbles, or solids, such as particles, may be contained within the liquid.

[0146] The liquid cleaning compositions of the present invention preferably have a viscosity of 50 to 10000 mPa·s, the liquid hand dishwashing compositions (liquid hand dishwashing compositions (manual "dish wash compositions") preferably have a viscosity of 100 to 10000 mPa·s, more preferably 200 to 5000 mPa·s, and most preferably 500 to 3000 mPa·s, at 20 1 / s and 20°C, and the liquid laundry cleaning compositions preferably have a viscosity of 50 to 3000 mPa·s, more preferably 100 to 1500 mPa·s, and most preferably 200 to 1000 mPa·s, at 20 1 / s and 20°C.

[0147] The liquid cleaning composition of the present invention may have any suitable pH value. Preferably, the pH of the composition is adjusted to 4-14. More preferably, the composition has a pH of 6-13, even more preferably 6-10, and most preferably 7-9. The pH of the composition may be adjusted using pH adjusting ingredients known in the art, measured at a product concentration of 10% in demineralized water at 25°C. For example, NaOH may be used, the actual weight % of NaOH may vary, and a desired pH, such as pH 8.0, may be achieved. In one embodiment of the present invention, the pH may be adjusted to above 7 by using amines, preferably alkanolamines, more preferably triethanolamine.

[0148] Detergent compositions, such as fabric care and home care products and commercial and institutional cleaning formulations, more specifically laundry and hand dish detergents, are known to those skilled in the art. Any compositions, etc., known to those skilled in the art related to the respective applications, can be used in the context of the present invention by including at least one of the polymers of the present invention, preferably at least one of the polymers, in an amount suitable for expressing specific properties in such compositions, especially when such compositions are used in their field of use.

[0149] An aspect of the present invention is also the use of the polymers of the present invention in detergent formulations, in particular liquid detergent formulations, preferably concentrated liquid detergent formulations or as single doses for laundry.

[0150] The cleaning compositions of the present invention may, and preferably do, contain auxiliary cleaning additives (sometimes abbreviated herein as "adjuncts"), such adjuncts being preferably in addition to the surfactant system defined above.

[0151] Suitable auxiliary cleaning additives include builders, co-builders, surfactant systems, fatty acids and / or their salts, structurants, thickeners and rheology improvers, viscosity / stain removal / anti-redeposition agents, polymeric soil release agents, dispersants such as polymeric dispersants, polymeric degreasers, solubilizers, amphiphilic copolymers (including those without vinylpyrrolidone), chelating agents, enzymes, enzyme stabilization systems, encapsulated benefit agents such as encapsulated fragrances, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, catalytic materials, brighteners, malodor control agents, pigments, dyes, opacifiers, pearlescent agents, hueing agents, dye transfer inhibitors, fabric softeners, carriers, suds boosters, suds suppressors (defoamers), color speckle, silver care (silver care), and the like. care), rust and / or corrosion inhibitors, alkalinity sources, pH adjusters, pH buffers, hydrotropes, scrubbing particles, antibacterial and antimicrobial agents, preservatives, antioxidants, softening agents, carriers, fillers, solvents, processing aids, pro-fragrance, and fragrances.

[0152] Adjuvants may be present in the composition at levels suitable for the intended use of the composition, with typical usage levels ranging from as low as 0.001% by weight of the composition for adjuvants such as optical brighteners, up to 50% by weight of the composition for builders.

[0153] The liquid cleaning composition may additionally comprise, and preferably does comprise, at least one of the following - a rheology control / regulator, an emollient, a moisturizer, a skin rejuvenation active, and a solvent - in addition to the surfactant system and the grafted polymer.

[0154] The solid composition may additionally comprise, and preferably does comprise, at least one of a filler, a bleaching agent, a bleach activator, and a catalytic material.

[0155] Suitable examples of such cleaning adjuvants and amounts used are described in WO 99 / 05242, U.S. Pat. No. 5,576,282, U.S. Pat. No. 6,306,812 B1 and U.S. Pat. No. 6,326,348 B1.

[0156] Those skilled in the art will appreciate that a detersive surfactant includes any surfactant or mixture of surfactants that is useful in cleaning, removing stains or laundering soiled materials.

[0157] Thus, cleaning compositions of the present invention, such as fabric care and home care products and institutional and corporate cleaning formulations, more particularly laundry and hand dish detergents, preferably additionally comprise a surfactant system as described above and in more detail below, and more preferably also comprise adjuvants.

[0158] The surfactant system can be composed of one surfactant or a combination of surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. Those skilled in the art will appreciate that a detergent surfactant system includes any surfactant or mixture of surfactants that is beneficial for cleaning, removing stains, or laundering soiled materials.

[0159] The cleaning compositions of the present invention preferably comprise 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% of the surfactant system by weight of the composition. In further embodiments, the cleaning composition comprises from about 5% to about 30% of the surfactant system by weight of the composition. The surfactant system may comprise a cleaning surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof.

[0160] Laundry Compositions In laundry formulations, anionic surfactants usually make up the largest and by far the largest proportion of surfactants contained in such formulations.Thus, preferably, the cleaning composition of the present invention for use in laundry comprises at least one anionic surfactant and, optionally, a further surfactant selected from any of the surfactant classes described herein, preferably from nonionic surfactants and / or amphoteric surfactants and / or zwitterionic surfactants and / or cationic surfactants.

[0161] Non-limiting examples of anionic surfactants, which may also be used in combinations of two or more surfactants useful herein, include C9-C20 linear alkyl benzene sulfonates (LAS), C10-C20 primary, branched and random alkyl sulfates (AS); C10-C18 These include secondary (2,3) alkyl sulfates; C10-C18 alkyl alkoxy sulfates (AExS) (x is 1-30); C10-C18 alkyl alkoxy carboxylates containing 1-5 ethoxy units; internally branched alkyl sulfates as described in U.S. Pat. Nos. 6,020,303 and 6,060,443; internally branched alkyl alkoxy sulfates as described in U.S. Pat. Nos. 6,008,181 and 6,020,303; modified alkyl benzene sulfonates (MLAS) as described in WO 99 / 05243, WO 99 / 05242 and WO 99 / 05244; methyl ester sulfonates (MES); and alpha-olefin sulfonates (AOS).

[0162] Non-limiting examples of non-ionic surfactants that may also be used in combination with two or more other surfactants include: C8-C18 alkyl ethoxylates, such as NEODOL®, a non-ionic surfactant from Shell; ethylene oxide / propylene oxide block alkoxylates, such as PLURONIC® from BASF; C14-C22 internally branched alkyl alkoxylates, such as those described in U.S. Pat. Nos. 6,153,577, 6,020,303, and 6,093,856. BAEx (x is 1-30); the alkyl polysaccharides described in U.S. Pat. No. 4,565,647, issued Jan. 26, 1986 to Llenado; specifically, the alkyl polyglycosides described in U.S. Pat. Nos. 4,483,780 and 4,483,779; the polyhydroxy fatty acid amides described in U.S. Pat. No. 5,332,528; and the ether-terminated poly(oxyalkylated) alcohol surfactants described in U.S. Pat. No. 6,482,994 and WO 01 / 42408.

[0163] Non-limiting examples of amphoteric surfactants that may be used in combination with one or more surfactants include: water-soluble amine oxides containing one alkyl moiety having about 8 to about 18 carbon atoms and two moieties selected from the group consisting of alkyl moieties and hydroxyalkyl moieties containing about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety having about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl moieties and hydroxyalkyl moieties containing about 1 to about 3 carbon atoms. See WO 01 / 32816, U.S. Pat. No. 4,681,704 and U.S. Pat. No. 4,133,779. Suitable surfactants include so-called amine oxides, such as lauryl dimethylamine oxide ("lauramine oxide").

[0164] The cleaning compositions may also include zwitterionic surfactants, which may also be used in combination with two or more other surfactants.

[0165] Suitable zwitterionic surfactants include betaines, such as alkyl betaines, alkyl amido betaines, amido azolinium betaines, sulfo betaines (INCI: sultaines), as well as phospho betaines. Suitable betaines and sulfo betaines are as follows (listed according to INCI): almond amidopropyl betaine, apricot amidopropyl betaine, avocado amidopropyl betaine, babassu amidopropyl betaine, behenamidopropyl betaine, behenyl betaine, canola amidopropyl betaine, capryl / capramidopropyl betaine, carnitine, cetyl betaine, cocamidoethyl betaine, cocamidopropyl ... Pyr Hydroxysultaine, Coco Betaine, Coco Hydroxysultaine, Coco / Oleamidopropyl Betaine, Coco Sultaine, Decyl Betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Propyl PG-Betaine, Erucamidopropyl Hydroxysultaine, Hydrogenated Tallow Betaine, Isostearamidopropyl Betaine , lauramidopropyl betaine, lauryl betaine, lauryl hydroxysultaine, lauryl sultaine, milkamidopropyl betaine, minkamidopropyl betaine, myristamidopropyl betaine, myristyl betaine, oleamidopropyl betaine, oleamidopropyl hydroxysultaine, oleyl betaine, oliamidopropyl betaine, coconutamidopropyl betaine, palmitamidopropyl betaine, palmitoyl carnitine, coconut kernel amidopropyl betaine, polytetrafluoroethylene acetoxypropyl betaine, ricinoleamidopropyl betaine, sesamidopropyl betaine, soyamidopropyl betaine, stearamidopropyl betaine, stearyl betaine, tallowamidopropyl betaine, tallowamidopropyl hydroxysultaine, tallow betaine, tallow dihydroxyethyl betaine, undecylenamidopropyl betaine, and wheat germ amidopropyl betaine.

[0166] Preferred betaines are, for example, C 12 ~C 18 Alkyl betaines and sulfobetaines. The zwitterionic surfactant is preferably a betaine surfactant, more preferably a cocoamidopropyl betaine surfactant.

[0167] Non-limiting examples of cationic surfactants that may also be used in combination with two or more other surfactants include: quaternary ammonium surfactants, which may have up to 26 carbon atoms, such as the alkoxylated quaternary ammonium (AQA) surfactants described in U.S. Pat. No. 6,136,769; dimethylhydroxyethyl quaternary ammonium, described in U.S. Pat. No. 6,004,922; dimethylhydroxyethyl lauryl ammonium chloride, described in WO 98 / 35002, WO 98 / 35003, WO 98 / 35004, WO 98 / 35005, WO 98 / 35006, WO 98 / 35007, WO 98 / 35009, WO 98 / 35010, WO 98 / 35011, WO 98 / 35012, WO 98 / 35013, WO 98 / 35014, WO 98 / 35015, WO 98 / 35016, WO 98 / 35017, WO 98 / 35018, WO 98 / 35019 ... polyamine cationic surfactants as described in WO 98 / 35004, WO 98 / 35005 and WO 98 / 35006; cationic ester surfactants as described in U.S. Pat. Nos. 4,228,042, 4,239,660, 4,260,529 and 6,022,844; and amino surfactants as described in U.S. Pat. No. 6,221,825 and WO 00 / 47708, particularly amidopropyldimethylamine (APA).

[0168] The composition according to the invention may comprise at least one builder. In the context of the present invention, no distinction is to be made between builders and components elsewhere called "co-builders". Examples of builders are complexing agents, also called complexing agents hereafter, ion exchange compounds, dispersants, scale inhibitors and precipitants. The builders are selected from citrates, phosphates, silicates, carbonates, phosphonates, aminocarboxylates and polycarboxylates.

[0169] In one embodiment of the invention, the builder is selected from polycarboxylates. The term "polycarboxylate" refers to succinic acid, C2-C 16 Alkyl disuccinates, C2-C 16 These include non-polymeric polycarboxylates such as alkenyl disuccinates, ethylenediamine N,N'-disuccinate, tartrate diacetate, alkali metal malonate, tartrate monoacetate, propanetricarboxylic acid, butanetetracarboxylic acid, and cyclopentanetetracarboxylic acid.

[0170] Oligomeric or polymeric polycarboxylates are, for example, polyaspartic acid and its alkali metal salts, in particular its sodium salt, (meth)acrylic acid homopolymers and (meth)acrylic acid copolymers and their alkali metal salts, in particular their sodium salts.

[0171] Suitable comonomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid, and citraconic acid. Suitable polymers are preferably, in particular, those having a weight average molecular weight M w in the range from 2000 to 40000 g / mol, preferably from 2000 to 10000 g / mol, in particular from 3000 to 8000 g / mol. Further suitable polycarboxylate copolymers are in particular copolymers of acrylic acid and methacrylic acid and copolymers of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid or their anhydrides, such as maleic anhydride. Suitable copolymers are in particular copolymers of acrylic acid and maleic acid with a weight-average molecular weight Mw in the range from 2000 to 100000, preferably from 3000 to 80000.

[0172] The weight average molecular weight Mw of the polyaspartic acid is preferably in the range of 1000 g / mol to 20000 g / mol, more preferably 1500 to 15000 g / mol, and particularly preferably 2000 to 10000 g / mol.

[0173] The formulation according to the invention may contain one or more alkaline carriers. The alkaline carriers ensure, for example, a pH of at least 9 if an alkaline pH is desired. For example, the above-mentioned alkali metal carbonates, alkali metal hydrogen carbonates and alkali metal metasilicates, and additionally alkali metal hydroxides, are suitable. In each case, the preferred alkali metal is potassium, with sodium being particularly preferred. In one embodiment of the present invention, a pH of more than 7 may be adjusted by using amines, preferably alkanolamines, more preferably triethanolamine.

[0174] In one embodiment of the invention, the laundry formulation of the present invention additionally comprises at least one enzyme.

[0175] Useful enzymes are, for example, one or more hydrolases selected from lipases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, and peroxidases, as well as combinations of at least two of the above classes.

[0176] Such enzymes may be incorporated at a level sufficient to provide an effective amount of cleaning. A preferred amount is in the range of 0.001% to 5% active enzyme by weight of the detergent composition of the present invention. Enzyme stabilizing systems may also be used in conjunction with the enzymes, such as calcium ions, boric acid, boronic acid, propylene glycol, and short chain carboxylic acids. In the context of the present invention, short chain carboxylic acids are selected from monocarboxylic acids containing 1 to 3 carbon atoms per molecule and dicarboxylic acids containing 2 to 6 carbon atoms per molecule. Preferred examples are formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, HOOC(CH2)3COOH, adipic acid and mixtures of at least two of the above, as well as the respective sodium and potassium salts.

[0177] Preferably, the at least one enzyme is a detergent enzyme.

[0178] In one embodiment, the enzyme is classified as an oxidoreductase (EC 1), transferase (EC 2), hydrolase (EC 3), lyase (EC 4), isomerase (EC 5), or ligase (EC 6). This EC number assignment is in accordance with the Enzyme Nomenclature, Recommendations, Nomenclature Committee of the International Union of Biochemistry and Molecular Biology (1992), including addenda published in 1993-1999. Preferably, the enzyme is a hydrolase (EC 3).

[0179] In a preferred embodiment, the enzyme is: Protease, amylase, lipase, cellulase, mannanase, hemicellulase, phospholipase, esterase, pectinase, lactase, peroxidase, xylanase, cutinase, pectate lyase, keratinase, reductase, oxidase, phenoloxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, beta-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, nuclease, deoxyribonuclease, phosphodiesterase, phytase, carbohydrase The enzyme is selected from the group consisting of enzymes ... Most preferably, the enzyme is a protease, preferably a serine protease, more preferably a subtilisin protease.

[0180] Preferably, the protease is a protease with at least 90% sequence identity to SEQ ID NO: 22 of EP1921147B1 and with the amino acid substitution R101E (according to the BPN residue numbering). Preferably, the amylase is an amylase with at least 90% sequence identity to SEQ ID NO: 54 of WO2021032881A1.

[0181] The compositions of the invention may contain one type of enzyme, or two or more enzymes of different types, such as an amylase and a protease, or two or more enzymes of the same type, such as two or more different proteases, or mixtures thereof, such as an amylase and two different proteases.

[0182] The enzyme may be incorporated into the composition at a level sufficient to provide an effective amount to achieve a beneficial effect, preferably a primary cleaning effect and / or a secondary cleaning effect such as an anti-blackening or anti-pilling effect (e.g., in the case of cellulases). Preferably, the enzyme is present in the composition at a level such that the enzyme protein is from about 0.00001% to about 5%, preferably from about 0.00001% to about 2%, more preferably from about 0.0001% to about 1%, and even more preferably from about 0.001% to about 0.5% by weight of the composition.

[0183] Preferably, the enzyme-containing composition further comprises an enzyme stabilization system.

[0184] Preferably, the enzyme-containing compositions described herein comprise from about 0.001% to about 10%, from about 0.005% to about 8%, or from about 0.01% to about 6% of an enzyme stabilization system by weight of the composition. The enzyme stabilization system can be any stabilization system compatible with the enzyme.

[0185] Preferably, the enzyme stabilization system comprises at least one compound selected from the group consisting of a polyol (preferably 1,3-propanediol, ethylene glycol, glycerol, 1,2-propanediol or sorbitol), an inorganic salt (preferably CaCl2, MgCl2 or NaCl), a short-chain (preferably C1-C3) carboxylic acid or a salt thereof (preferably formic acid, a formate (preferably sodium formate), acetic acid, an acetate or a lactate), a borate, boric acid, a boronic acid (preferably 4-formylphenylboronic acid (4-FPBA)), a peptide aldehyde, a peptide acetal and a peptide aldehyde hydrosulfite adduct. Preferably, the enzyme stabilization system comprises a combination of at least two compounds selected from the group consisting of salts, polyols and short chain carboxylic acids, preferably one or more compounds selected from the group consisting of borate, boric acid, boronic acid (preferably 4-formylphenylboronic acid (4-FPBA)), peptide aldehyde, peptide acetal and peptide aldehyde hydrosulfite adduct. In particular, when a protease is present in the composition, a protease inhibitor preferably selected from borate, boric acid, boronic acid (preferably 4-FPBA), peptide aldehyde (preferably a peptide aldehyde such as Z-VAL-H or Z-GAY-H), peptide acetal and peptide aldehyde hydrosulfite adduct can be added.

[0186] The compositions according to the invention may contain one or more bleaching agents.

[0187] The formulation according to the invention comprises one or more Bleaching catalyst may include. The formulation according to the invention comprises one or more bleach activator may include. Formulations according to the invention may include one or more corrosion inhibitors.

[0188] The formulations according to the invention may also comprise further cleaning polymers and / or soil release polymers and / or soil prevention polymers.

[0189] Additional cleaning polymers may include, but are not limited to, "multifunctional polyethyleneimines" (e.g., Sokalan® HP20 from BASF) and / or "multifunctional diamines" (e.g., Sokalan® HP96 from BASF). Such multifunctional polyethyleneimines typically have a weight average molecular weight M w In the range of 3000-250000 g / mol, preferably in the range of 5000-200000 g / mol, more preferably in the range of 8000-100000 g / mol, more preferably in the range of 8000-50000 g / mol, more preferably in the range of 10000-30000 g / mol, and most preferably in the range of 10000-20000 g / mol. Suitable polyfunctional polyethyleneimines have 80%-99% by weight of ethylene oxide side chains, preferably 85%-99% by weight, more preferably 90%-98% by weight, and most preferably 93%-97% by weight or 94%-96% by weight, based on the total weight of the material. Ethoxylated polyethyleneimines are typically based on a polyethyleneimine core and a polyethylene oxide shell. Suitable polyethyleneimine core molecules have a weight average molecular weight M w Preferably, the molecular weight is 500 to 1000 g / mol, and more preferably, M w is 600-800 g / mol. In that case, the ethoxylated polymer has on average 5-50, preferably 10-35, even more preferably 20-35 ethylene oxide (EO) units per NH functional group.

[0190] Suitable polyfunctional diamines are typically ethoxylated C2-C12 alkylene diamines, preferably hexamethylene diamine, which are further quaternized and optionally sulfated. The weight average molecular weight M of typical polyfunctional diamines is wis in the range of 2000 to 10000 g / mol, more preferably in the range of 3000 to 8000 g / mol, and most preferably in the range of 4000 to 6000 g / mol. In a preferred embodiment of the present invention, further quaternized and sulfated ethoxylated hexamethylenediamine can be used, which contains an average of 10 to 50, preferably 15 to 40, more preferably 20 to 30 ethylene oxide (EO) groups per NH group, and preferably has two cationic ammonium groups and two anionic sulfate groups.

[0191] In a preferred embodiment of the present invention, the cleaning composition may contain at least one polyfunctional polyethyleneimine and / or at least one polyfunctional diamine to improve the cleaning performance of the laundry detergent, preferably the soil removal ability, especially the primary cleaning power of particulate soils on polyester fabrics, etc. The polyfunctional polyethyleneimine or polyfunctional diamine or mixtures thereof according to the above description may be added to the laundry detergent and cleaning composition in a small amount of generally 0.05 to 15% by weight, preferably 0.1 to 10% by weight, more preferably 0.25 to 5% by weight, or even 2% by weight or less, based on the total specific composition including other ingredients and water and / or solvent.

[0192] Suitable further polyfunctional polyethyleneimines, polyfunctional diamines and oligoamines include those claimed in WO 2022 / 136408 A1, WO 2022 / 136409 A1, and WO 2021 / 165468.

[0193] Thus, one aspect of the present invention is a laundry detergent composition, in particular a liquid laundry detergent, comprising (i) at least one polymer of the present invention and (ii) at least one compound selected from multifunctional polyethyleneimines and multifunctional di- and oligoamines, and mixtures thereof.

[0194] In one embodiment of the present invention, the ratio of the at least one polymer of the present invention to (ii) at least one compound selected from polyfunctional polyethyleneimines and polyfunctional diamines and oligoamines, and mixtures thereof, is 10:1 to 1:10, preferably 5:1 to 1:5, more preferably 3:1 to 1:3.

[0195] Suitable dark stain preventing polymers include copolymers of acrylic acid or maleic acid and styrene, graft polymers of acrylic acid onto maltodextrin or carboxymethylated cellulose and their alkali metal salts, especially their sodium salts.

[0196] Laundry formulations containing the polymers of the present invention may also contain at least one complexing agent.

[0197] Preferred complexing agents are methylglycine diacetate (MGDA) and glutamic acid diacetate (GLDA) and their salts. Particularly preferred complexing agents are methylglycine diacetate and its salts. According to the present invention, the complexing agent is present in an amount of 1 to 50% by weight, preferably 1 to 20% by weight.

[0198] Laundry formulations containing the polymers of the present invention may also contain at least one antimicrobial agent.An antimicrobial agent is a compound that kills or inhibits the growth or reproduction of microorganisms.The microorganisms may be bacteria, yeasts or molds.Preservatives are antimicrobial agents that can be added to aqueous products and compositions to maintain the original performance, properties and integrity of the products and compositions by killing or inhibiting the growth of contaminating microorganisms.

[0199] The composition / formulation may contain one or more antimicrobial agents and / or preservatives listed on pages 35-39 of WO 2021 / 115912 A1 ("Formulations comprising a hydrophobically modified polyethyleneimine and one or more enzymes").

[0200] Any of the following antimicrobial and / or preservative agents are of particular interest for cleaning compositions and fabric care and home care products, specifically for laundry formulations: 4,4'-Dichloro-2-hydroxydiphenyl ether (other names: 5-chloro-2-(4-chlorophenoxy)phenol (Diclosan, DCPP), Tinosan® HP 100 (30% by weight of DCPP in 1,2-propylene glycol);2-phenoxyethanol (other names: phenoxyethanol, methylphenyl glycol, phenoxetol, ethylene glycol phenyl ether, ethylene glycol monophenyl ether, 2-(phenoxy)ethanol, 2-phenoxy-1-ethanol);2-bromo-2-nitropropane-1,3-diol (other names: 2-bromo-2-nitro-1,3-propanediol, bronopol);glutaraldehyde (other names: 1,5-pentanedial, pentane-1,5-dial, glutaral, glutaric dialdehyde);glyoxal (other names: ethanedial, oxyaldehyde, 1,2-ethanedial);5-bromo-5-nitro-1,3 -Dioxane (other names: 5-bromo-5-nitro-m-dioxane, Bronidox®);Phenoxypropanol (other names: Propylene glycol phenyl ether, Phenoxyisopropanol 1-phenoxy-2-propanol, 2-phenoxy-1-propanol);Glucoprotamine (chemical description: reaction product of glutamic acid and alkylpropylenediamines, other names: Glucoprotamine 50);Cyclohexylhydroxyldiazenium-1-oxide, potassium salt (other names: N-cyclohexyl-diazenium dioxide, potassium HDO, Xyligene);Formic acid (other names: Methanoic acid, Protectol® FM, Protectol® FM 75, Protectol® FM 85, Protectol® FM 99, Lutensol® FM) and its salts (e.g., sodium formate); tetrahydro-3,5-dimethyl-1,3,5-thiadiazine-2-thione (other names: 3,5-dimethyl-1,3-5-thiadiazinan-2-thione, dazomet; 2,4-dichlorobenzyl alcohol (other names: dichlorobenzyl alcohol, 2,4-dichloro-benzenemethanol, (2,4-dichloro-phenyl)-methanol, DCBA);1-Propanol (other names: n-propanol, propan-1-ol, n-propyl alcohol); 1,3,5-tris-(2-hydroxyethyl)-hexahydro-1,3,5-triazine (other names: hexyhydrotriazin, tris(hydroethyl)-hexyhydrotriazine, hexyhydro-1,3-5-tris(2-hydroxyethyl)-s-to 2-Butyl-benzo[d]isothiazol-3-one ("BBIT"); 2-Methyl-2H-isothiazol-3-one ("MIT"); 2-Octyl-2H-isothiazol-3-one ("OIT"); 5-Chloro-2-methyl-2H-isothiazol-3-one ("CIT" or "CMIT"); 5-Chloro-2-methyl-2H-isothiazol mixtures of 2-methyl-2H-isothiazol-3-one ("CMIT") and 2-methyl-2H-isothiazol-3-one ("MIT") (mixtures of CMIT / MIT); 1,2-benzisothiazol-3(2H)-one ("BIT"); hexa-2,4-dienoic acid (commonly known as "sorbic acid") and its salts, e.g., calcium sorbate, sodium sorbate; (E,E)-potassium hexa-2,4-dienoate (potassium sorbate); lactic acid and its salts; L-(+)-lactic acid; in particular sodium lactate. sodium;benzoic acid and its salts such as sodium benzoate, ammonium benzoate, calcium benzoate, magnesium benzoate, MEA-benzoic acid, potassium benzoate;salicylic acid and its salts such as calcium salicylate, magnesium salicylate, MEA salicylate, sodium salicylate, potassium salicylate, TEA salicylate;benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate;didecyldimethylammonium chloride ("DDAC");N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine ("diamine");peracetic acid;hydrogen peroxide.;

[0201] At least one antimicrobial agent or preservative may be added to the composition of the present invention at a concentration of 0.001 to 10% by weight of the total composition.

[0202] Preferably, the composition contains 2-phenoxyethanol at a concentration of 0.1 to 2% or 4,4'-dichloro 2-hydroxydiphenyl ether (DCPP) at a concentration of 0.005 to 0.6%.

[0203] The laundry formulations of the present invention may contain at least one antimicrobial agent from the list above and / or combinations thereof and / or combinations with at least one further antimicrobial agent not mentioned in this list.

[0204] Formulations according to the invention may also contain water and / or additional organic solvents, for example ethanol or propylene glycol, and / or fillers such as sodium sulfate.

[0205] Further optional ingredients may be, but are not limited to, viscosity modifiers, cationic surfactants, foam boosters or foam reducing agents, fragrances, dyes, optical brighteners and color transfer inhibitors.

[0206] Dishwashing Composition Another aspect of the present invention is also a dishwashing composition comprising at least one of the inventive polymers described above.

[0207] Thus, an aspect of the present invention is also the use of the inventive polymers described above in dishwashing applications, such as hand or automatic dishwashing applications.

[0208] The dishwashing compositions of the present invention may be in the form of liquid, semi-liquid, cream, lotion, gel, or solid compositions, with solid embodiments including, for example, powders and tablets. Liquid compositions are typically suitable for hand dishwashing applications, while solid and pouch formulations (pouches may contain solids in addition to liquid components) are typically suitable for automatic dishwashing compositions, although in some parts of the world, liquid automatic dishwashing compositions are also used, and therefore are of course also encompassed by the term "dishwashing composition."

[0209] Dishwashing compositions are intended for direct or indirect application to tableware and metal and glass surfaces, including drinking and other glasses, beakers, dishes, and cooking utensils such as pots and pans, and cutlery such as forks, spoons, knives, and the like.

[0210] The method of the present invention for cleaning dishware, metal, and / or glass surfaces comprises the step of applying a dishwashing cleaning composition, preferably in liquid form, directly or with a cleaning implement (i.e., in undiluted form) to the surface. The composition is applied directly to the surface to be treated without significant dilution (neat) prior to application and / or to a cleaning implement or tool, such as a dish cloth, sponge, or dishwashing brush. The cleaning implement or tool is preferably moistened before or after the composition is delivered. In the method of the present invention, the composition can also be applied in diluted form.

[0211] The formulations of the invention, which contain at least one inventive polymer, exhibit excellent cleaning performance, i.e., extremely good degreasing properties, whether applied neat or diluted. The presence of the inventive polymer reduces the effort required to remove greasy and / or oily soils from dishware, metal and / or glass surfaces, even if a lower amount of surfactant is used than in conventional compositions.

[0212] Preferably, the compositions are formulated to provide superior grease cleaning (degreasing) performance, long lasting foam, and / or improved viscosity control when exposed to low temperatures, preferably at least two and more preferably all three of these performance attributes are present in the dishwashing compositions of the present invention. Optional - and preferably present - additional benefits of the hand dishwashing compositions of the present invention include stain removal, shine, and / or hand protection, more preferably at least two and most preferably all three of these additional benefits are present in the dishwashing compositions of the present invention.

[0213] In one embodiment of the invention, the polymer of the present invention is a component of a hand dishwashing formulation additionally comprising at least one surfactant, preferably at least one anionic surfactant.

[0214] In another embodiment of the present invention, the polymer of the present invention is a component of a hand dishwashing formulation additionally comprising at least one anionic surfactant and at least one other surfactant, preferably selected from amphoteric and / or zwitterionic surfactants. In a preferred embodiment of the present invention, the hand dishwashing formulation comprises at least one amphoteric surfactant, preferably an amine oxide, or at least one zwitterionic surfactant, preferably a betaine, or a mixture thereof, to aid in the foaming, cleaning power and / or mildness of the detergent composition.

[0215] Examples of suitable anionic surfactants are as already described above in relation to the laundry compositions.

[0216] The dishwashing compositions of the present invention may include at least one amphoteric surfactant. The addition of an amphoteric surfactant provides good foaming properties in the dishwashing composition.

[0217] The dishwashing compositions of the present invention may include at least one zwitterionic surfactant.

[0218] The dishwashing compositions of the present invention may comprise at least one cationic surfactant.

[0219] The dishwashing composition according to the present invention may comprise at least one non-ionic surfactant.

[0220] The dishwashing compositions according to the present invention may contain an effective amount of at least one hydrotrope to ensure compatibility of the liquid hand dishwashing detergent composition with water.

[0221] The dishwashing composition according to the present invention may comprise at least one organic solvent.

[0222] The dishwashing composition according to the present invention may comprise at least one electrolyte.

[0223] Hand dishwashing formulations containing the polymers of the present invention may also contain at least one antimicrobial agent.

[0224] Examples of antimicrobial agents suitable for dishwashing compositions are as already described above for laundry compositions.

[0225] Antimicrobial agents may be added to the hand dishwashing compositions of the present invention at a concentration of 0.0001% to 10% by weight, based on the total weight of the composition. Preferably, the formulation contains 2-phenoxyethanol at a concentration of 0.01% to 5%, more preferably 0.1% to 2%, and / or 4,4'-dichloro-2-hydroxydiphenyl ether at a concentration of 0.001% to 1%, more preferably 0.002% to 0.6%, based on the total weight of the composition (in all cases).

[0226] Further ingredients include, but are not limited to, conditioning polymers, cleaning polymers, surface modifying polymers, soil flocculating polymers, rheology modifying polymers, enzymes, structurants, builders, chelating agents, cyclic diamines, emollients, moisturizers, skin rejuvenation actives, carboxylic acids, scrubbing particles, bleaches and bleach activators, fragrances, malodor control agents, pigments, dyes, opacifiers, beads, pearlescent particles, microcapsules, antimicrobial agents, pH adjusters such as NaOH, alkanolamines such as monoethanolamine, buffering means, and the like.

[0227] Examples of suitable and preferred ingredients mentioned above as ingredients for dishwashing compositions have already been described above in relation to laundry compositions.

[0228] Common cleaning compositions and formulations Since the polymers of the invention are biodegradable and, in particular, the pH of cleaning formulations is usually about 7 or higher, and in addition, such cleaning formulations often also contain enzymes for the purpose of decomposing biodegradable materials such as grease, proteins, polysaccharides, etc., present in stains and dirt, which need to be removed by the cleaning composition, it is necessary to take into account the formulation of the biodegradable polymers of the invention in some way.Such suitable formulations are known in principle and include solid as well as liquid and semi-liquid formulations, in the case of solids, the enzymes and the polymers can be added separately in a coating or mixed as separate particles, and in the case of liquids and semi-liquids, the polymers and the enzymes can be separately formulated in different compartments, for example in different compartments of a multi-chamber pouch or a multi-chamber bottle, from which a predetermined amount of liquid is poured out simultaneously to ensure that each component is applied in the correct amount according to the individual point of use.Such multi-chamber pouches, bottles, etc. are also known to those skilled in the art.

[0229] The liquid formulations disclosed in this section may contain 0-2%, preferably about 1%, of 2-phenoxyethanol in addition to all other ingredients mentioned.

[0230] The liquid formulations disclosed above and below may contain, in addition to all other ingredients mentioned, 0-0.2%, preferably about 0.15%, of 4,4'-dichloro 2-hydroxydiphenyl ether. The bleach-free solid laundry compositions may contain, in addition to all other ingredients mentioned, 0-0.2%, preferably about 0.15%, of 4,4'-dichloro 2-hydroxydiphenyl ether.

[0231] The formulations disclosed in this chapter may contain, in addition to all other ingredients mentioned, one or more enzymes selected from those disclosed herein above, more preferably a protease and / or an amylase, more preferably a protease having at least 90% sequence identity with SEQ ID NO: 22 of EP 1921147 B1 and having the amino acid substitution R101E (according to the numbering of BPN residues), and the amylase having at least 90% sequence identity with SEQ ID NO: 54 of WO 2021032881 A1, such enzymes are preferably present in the formulation at a level such that the enzyme protein is from about 0.00001% to about 5%, preferably from about 0.00001% to about 2%, more preferably from about 0.0001% to about 1%, and even more preferably from about 0.001% to about 0.5% by weight of the composition.

[0232] The compositions shown below, including those in the table, disclose certain types of general cleaning compositions that represent typical compositions corresponding to typical cleaning conditions commonly employed in different regions and countries of the world. At least one inventive polymer may be added to such formulations in a suitable amount as outlined herein.

[0233] The compositions shown here that do not contain the grafted polymer of the present invention are comparative compositions, and are considered to be within the scope of the present invention when they contain the grafted polymer of the present invention, particularly in amounts within the ranges described herein as preferred, more preferred, etc.

[0234] In a preferred embodiment, the grafted polymers according to the present invention are used in laundry detergents.

[0235] The liquid laundry detergent according to the present invention comprises: 0.05 to 20% of at least one polymer of the present invention; Surfactant 1-50% Builder, cobuilder and / or chelating agent in an amount of 0.1 to 40%; Other auxiliary substances are 0.1 to 50%. The amount of water that makes the whole 100% and It consists of:

[0236] Preferred liquid laundry detergents according to the present invention include: 0.5 to 15% of at least one polymer of the present invention; 5 to 40% of an anionic surfactant selected from C10 to C15-LAS and C10 to C18 alkyl ether sulfates containing 1 to 5 ethoxy units; 1.5 to 10% of a nonionic surfactant selected from C10 to C18 alkyl ethoxylates containing 3 to 10 ethoxy units; 2-20% of a soluble organic builder / cobuilder selected from C10-C18 di- and tricarboxylic acids, hydroxydi- and hydroxytricarboxylic acids, aminopolycarboxylates, and polycarboxylic acids; 0.05 to 5% of an enzyme system comprising at least one enzyme suitable for detergents and preferably further comprising an enzyme stabilizing system; 0.5 to 20% of a mono- or diol selected from ethanol, isopropanol, ethylene glycol, or propylene glycol; Other additives at 0.1-20% The amount of water that makes the whole 100% and It consists of:

[0237] The solid laundry detergent according to the present invention (e.g. as a powder, granule or tablet) comprises: 0.2 to 20% of at least one polymer of the present invention; Surfactant 1-50% Builder, cobuilder and / or chelating agent in an amount of 0.1 to 90%; Filler is 0-50%. 0-40% bleach activator, 0.1-30% of other auxiliary substances and / or water, It is composed of The sum of the ingredients equals 100%.

[0238] Preferred solid laundry detergents according to the present invention include: 0.5 to 10% of at least one of the polymers of the present invention; 5 to 30% of an anionic surfactant selected from C10-C15-LAS, C10-C18 alkyl sulfates and C10-C18 alkyl ether sulfates containing 1 to 5 ethoxy units; 1.5 to 7.5% of a nonionic surfactant selected from C10 to C18 alkyl ethoxylates containing 3 to 10 ethoxy units; 20 to 80% of inorganic builders and fillers selected from sodium carbonate, sodium bicarbonate, zeolite, soluble silicates, and sodium sulfate; 0.5 to 15% of a cobuilder selected from C10 to C18 fatty acids, di- and tricarboxylic acids, hydroxydi- and hydroxytricarboxylic acids, aminopolycarboxylates, and polycarboxylic acids; 0.1 to 5% of an enzyme system comprising at least one enzyme suitable for detergents and preferably further comprising an enzyme stabilizing system; 0.5 to 30% bleach activator, Other additives at 0.1-20% The amount of water that makes the whole 100% and It consists of:

[0239] In a preferred embodiment, the polymers according to the present invention are used in hand dish detergents.

[0240] The liquid hand dish detergent according to the present invention comprises: 0.05 to 10% of at least one polymer of the present invention; Surfactant 1-50% Other auxiliary substances are 0.1 to 50%. The amount of water that makes the whole 100% and It consists of:

[0241] Preferred liquid hand dish detergents according to the present invention include: 0.2 to 5% of at least one polymer of the present invention; 5 to 40% of an anionic surfactant selected from C10 to C15-LAS, C10 to C18 alkyl ether sulfates containing 1 to 5 ethoxy units, and C10 to C18 alkyl sulfates; Cocamidopropyl betaine 2 10% Lauramine oxide 0-10% A non-ionic surfactant, preferably a C10 Guerbet alcohol alkoxylate, at 0-2%; 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; Other additives at 0.1-20% The amount of water that makes the whole 100% and It consists of:

[0242] General formulations (wt%) for laundry cleaning compositions according to the present invention

[0243] [Table 1]

[0244] Liquid laundry framework formulation according to the present invention: (wt%)

[0245] [Table 2]

[0246] Powder framework formulation for laundry according to the present invention: (wt%)

[0247] [Table 3]

[0248] Further exemplary liquid detergent formulations LD1, LD2 and LD3 are shown in the following three tables: (all values ​​in wt. %) [All three tables below: * "Grafted polymer" = (polyethylene glycol with Mn 6000 g / mol as graft substrate, grafted with 60% by weight of vinyl acetate (based on total polymer weight; produced according to the general disclosure of WO2007138054A1)]

[0249] Liquid Detergent 1- LD1 "Superior" Detergent

[0250] [Table 4]

[0251] Liquid detergent 2- LD2 "medium" performance detergent

[0252] [Table 5]

[0253] Liquid Detergent 3- LD3 "Medium" Performance Bio-Based Detergent

[0254] [Table 6]

[0255] Liquid hand dishwashing framework formulation according to the present invention: (wt%)

[0256] [Table 7]

[0257] In each laundry detergent, dishwashing composition, cleaning composition, and / or fabric care and home care product, the at least one grafted polymer is preferably present in a concentration, by weight % relative to the total weight of such composition or product, of from about 0.01% to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1% to about 10%, and most preferably from about 0.5% to about 5%, respectively, including all values ​​therebetween and all ranges obtained by combining any of the mentioned lower limits, further including 0.2, 0.3, 0.4, 1, 1, 5, 2, 2.5, 3, 3.5, and 4, with any of the mentioned upper limits, including 19, 18, 17, 16, 14, 13, 12, 11, 9, 8, 7, and 6.

[0258] The specific embodiments described throughout this disclosure are included as part of the present invention; various additional options disclosed herein as "optional," "preferred," "more preferred," "even more preferred," or "most preferred" options of a particular embodiment may be individually and independently selected (unless such independent selection is impossible due to the nature of the feature or unless such independent selection is expressly excluded) and combined within any other embodiment (where such other options and preferences may also be individually and independently selected), and each and every such possible combination is included as part of the present invention, as an individual embodiment.

[0259] Most Preferred Embodiments Section The following specific and most preferred embodiments in this section also form part of the present invention, and all combinations are defined within the individual embodiments, and all combinations therebetween expressly form part of the present invention.

[0260] In a first most preferred embodiment, the graft polymer of the present invention comprises: (A) a copolymer backbone as a graft substrate, said copolymer backbone (A) being obtainable by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide or 2,3-pentene oxide, a. the distribution of alkylene oxide moieties within the copolymer backbone is in random order; b. a copolymer backbone having a molecular weight Mn (g / mol) in the range of 500 to 7000, preferably 6000 or less, more preferably 5000 or less, even more preferably 4500 or less, even more preferably 4000 or less, even more preferably 3500 or less, even more preferably 3000 or less, most preferably 2500, preferably at least 1000, more preferably at least 1200; (B) polymeric side chains grafted onto the copolymer backbone, said polymeric side chains (B) being obtainable by polymerization of at least one vinyl ester monomer (B1) and optionally at least one other monomer (B2), and - if present - the weight ratio of monomer (B2) to monomer (B1) being less than 0.5, preferably less than 0.4, more preferably less than 0.3, even more preferably less than 0.2 and most preferably less than 0.1; A graft polymer comprising: In weight percent based on the total weight of the graft polymer, 25-85%, preferably 30-80%, more preferably 35-80%, even more preferably 40-75%, and most preferably 55-75% of the copolymer backbone (A); and a graft polymer containing 15 to 75%, preferably 20 to 70%, more preferably 20 to 65%, even more preferably 25 to 60%, and most preferably 25 to 45% of polymer side chains (B).

[0261] In yet a most preferred embodiment, the graft polymer of any of the aforementioned most preferred embodiments comprises i) is obtainable by polymerization of at least two monomers selected from the group ethylene oxide, 1,2-propylene oxide or 1,2-butylene oxide, preferably at least ethylene oxide is selected as one of the monomers, more preferably ethylene oxide and propylene oxide are selected as the only monomers, and / or ii) the relative amount of EO in the polymer backbone A is in the range of from 5 to 95%, preferably from 10 to 90%, more preferably from 15 to 85%, even more preferably from at least 20 to 80% (all expressed as weight percentage relative to the total mass of alkylene oxide in the polymer backbone (A)); and / or iii) Essentially no monomer (B2) is used in the polymerization to obtain the side chain (B). It comprises a copolymer backbone (A).

[0262] In a further most preferred embodiment, the graft polymer of any of the preceding most preferred embodiments comprises: i) has a polydispersity Mw / Mn of <5, preferably <3.5, more preferably <3, most preferably in the range of 1.0 to 2.5 (Mw=weight average molecular weight, Mn=number average molecular weight [g / mol / g / mol]); and / or ii) comprising a copolymer backbone (A) which is optionally end-capped at one or both end groups, preferably the copolymer backbone (A) is not end-capped at both end groups or, if the copolymer backbone (A) is end-capped, the end-capping is carried out by a C1-C25-alkyl group, preferably a C1-C4 group.

[0263] In a further most preferred embodiment, the graft polymer of any of the preceding most preferred embodiments comprises a polymeric side chain (B) obtained by radical polymerization in the presence of the polymeric backbone A of at least one vinyl ester monomer (B1) and optionally at least one other monomer (B2), Preferably at least 10 wt.-% of the total weight of vinyl ester monomers (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably vinyl acetate and vinyl laurate, most preferably vinyl acetate, the remaining amount of vinyl esters may be any other known vinyl ester, preferably at least 60, more preferably at least 70, even more preferably at least 80, even more preferably 90 wt.-% of vinyl acetate, most preferably essentially only vinyl acetate (i.e. about 100 wt.-% or even 100 wt.-% of vinyl acetate) is used as vinyl ester (wt.-% based on the total weight of vinyl ester monomers B1 used), Preferably essentially no monomer (B2) is used.

[0264] In a further most preferred embodiment, the graft polymer of any of the preceding most preferred embodiments is (A) 55-75% by weight (relative to the total weight of the graft polymer) of a copolymer backbone (A) obtainable by polymerization of ethylene oxide and 1,2-propylene oxide as alkylene oxide monomers, the alkylene oxide monomer distribution in the backbone being in random order, the molecular weight Mn (g / mol) of the copolymer backbone being in the range of 1200-2500, and the relative amount of EO in the polymer backbone (A) being 20-80% (by weight relative to the total mass of alkylene oxides in the polymer backbone (A)); (B) 25-45% by weight (based on the total weight of the grafted polymer) of polymer side chains grafted onto the copolymer backbone, derived from vinyl acetate as the only vinyl ester monomer (B1), essentially without the use of monomer (B2).

[0265] In a further most preferred embodiment, the grafted polymer of any of the preceding most preferred embodiments exhibits a biodegradability of the grafted polymer of at least 30, preferably at least 35, and even more preferably at least 40%, within 28 days when tested according to OECD 301F.

[0266] In a further most preferred embodiment, a process for obtaining a graft polymer as described in any of the embodiments detailed in the present disclosure, in particular as described in any of the most preferred embodiments above, is encompassed, which comprises polymerizing at least one vinyl ester monomer (B1) and optionally at least one further monomer (B2) in the presence of at least one copolymer backbone (A), a free radical-forming initiator (C) and, optionally, at most 50% by weight of at least one organic solvent (D), based on the sum of components (A), (B1), optionally (B2), (C) and (D), at an average polymerization temperature such that the decomposition half-life of the initiator (C) is between 40 and 500 minutes, in such a way that the proportion of unconverted graft monomer (B1) and optional monomer (B2) and initiator (C) in the reaction mixture is always kept quantitatively deficient with respect to the copolymer backbone (A).

[0267] In a further more preferred embodiment of the process detailed herein, including in particular the process of the previous paragraph, the process comprises polymerizing at least one vinyl ester monomer (B1) and optionally at least one other monomer (B2) in the presence of at least one polymer backbone (A), a free radical-forming initiator (C) and optionally at most 50% by weight of at least one organic solvent (D), based on the sum of components (A), (B1), optionally (B2) and (C), at an average polymerization temperature such that the decomposition half-life of the initiator (C) is between 40 and 500 minutes, in such a way that the proportion of unconverted grafting monomer (B1) and optionally (B2) and initiator (C) in the reaction mixture is always kept quantitatively deficient with respect to the polymer backbone (A), preferably at least 1% by weight of the total weight of the vinyl ester monomer (B1). % by weight is selected from vinyl acetate, vinyl propionate, and vinyl laurate, more preferably vinyl acetate and vinyl laurate, most preferably vinyl acetate, the remaining amount of vinyl esters can be any other known vinyl ester, preferably at least 60, more preferably at least 70, even more preferably at least 80, even more preferably at least 90% by weight of vinyl acetate, most preferably essentially only vinyl acetate (i.e. about 100% by weight or even 100% by weight of vinyl acetate) is used as vinyl ester (wt % based on the total weight of vinyl ester monomers B1 used), and - if (B2) is present - the weight ratio of optional monomer (B2) to monomer (B1) is less than 0.5, preferably less than 0.4, more preferably less than 0.3, even more preferably less than 0.2, most preferably less than 0.1.

[0268] In further most preferred embodiments of the process detailed herein, including in particular the most preferred embodiments of the process as detailed above, essentially no monomer (B2) is used in the process other than monomer (B1).

[0269] In further most preferred embodiments of the processes detailed herein, including in particular the most preferred embodiments of the processes as detailed above, the process comprises at least one further process step selected from i) to iv): i) post-polymerization; ii) purification; iii) concentration; and iv) drying.

[0270] In further most preferred embodiments of the processes detailed herein, including in particular the most preferred embodiments of the processes as detailed above, the process comprises at least one further process step selected from: i) a post-polymerization process step carried out after the main polymerization reaction, in which preferably a further amount of initiator (optionally dissolved in a solvent) is added over a period of from 0.5 hours up to 3 hours, preferably about 1-2 hours, more preferably about 1 hour, the radical initiator and the solvent for the initiator typically - and preferably - being the same as the solvent for the main polymerization reaction; after the polymerization reaction and before the post-polymerization reaction, preferably before starting the post-polymerization reaction by starting the addition of further radical initiator, a period of waiting is performed until the main polymerization reaction only proceeds, such period being preferably from 10 minutes up to 4 hours, preferably up to 2 hours, even more preferably up to 1 hour, most preferably up to 30 minutes; a process step in which the temperature of the post-polymerization process step - preferably - is the same as that of the main polymerization reaction or is increased, such increase being preferably by about 5-40°C, preferably by 10-20°C higher compared to the temperature of the main polymerization reaction; ii) subjecting the graft polymer obtained from the main polymerization or - if carried out - from a post-polymerization process - to a means of concentration and / or drying in order to remove part or almost all of the volatile substances such as residual solvents and / or residual monomers (as far as they can be removed due to their boiling points), a. Concentration is carried out by removing the solvent and optionally also a part of the volatile materials, preferably by applying a distillation process such as thermal or vacuum distillation, preferably vacuum distillation, to increase the solid polymer concentration until the desired solid content is achieved, preferably until the desired part or all of the volatile components such as volatile solvent and / or unreacted volatile monomers are removed; b. Drying is performed by subjecting the graft polymer, containing at least a residual amount of volatile substances such as residual solvent and / or unreacted monomers, to a means for removing volatile substances such as drying using a roller drum, spray drying, vacuum drying, or freeze drying, preferably - mainly for cost reasons - spray drying; optionally combining such a drying process step with a means of agglomeration or granulation to obtain agglomerated or granulated graft polymer particles, such processes being preferably selected from spray agglomeration, granulation, or drying in a fluidized bed dryer, spray granulator, etc.

[0271] In further most preferred embodiments of the processes detailed herein, including specifically the most preferred embodiments of the processes as detailed above, the amount of water is low, preferably less than 5% by weight, more preferably less than 1%, based on total solvent.

[0272] In a further most preferred embodiment, the grafted polymer of or obtained by any of the embodiments disclosed herein, in particular any of the aforementioned most preferred embodiments, is used as an ingredient in a composition or product that is a fabric care and home care product, a cleaning composition, an institutional and corporate cleaning product, a cosmetic or personal care product, an oil field formulation such as an emulsion breaker for crude oil, a pigment dispersion for inks such as inkjet inks, an electroplating product, a cement-based composition, a lacquer, a paint, or an agrochemical formulation, preferably a fabric care and home care composition or product, a cleaning composition, or an institutional and corporate cleaning product, more preferably a cleaning composition, most preferably a laundry detergent formulation, such fabric care and home care product, cleaning composition, institutional and corporate cleaning product, preferably further comprising at least one enzyme selected from one or more of lipase, hydrolase, amylase, protease, cellulase, hemicellulase, phospholipase, esterase, pectinase, lactase and peroxidase, as well as a combination of at least two of the aforementioned types.

[0273] In a further most preferred embodiment, the graft polymer of or obtained by any of the embodiments disclosed herein, in particular any of the most preferred embodiments mentioned above, is a composition, i.e. They are used in compositions that are fabric care and home care products, cleaning compositions, commercial and institutional cleaning products, cosmetics or personal care products, oil field formulations such as emulsion breakers for crude oil, pigment dispersions for inks such as inkjet inks, electroplating products, cementitious compositions, lacquers, paints, agrochemical formulations.

[0274] In a further most preferred embodiment of the aforementioned most preferred embodiment of the use of the grafted polymer, the grafted polymer of or obtained by any of the embodiments disclosed herein, in particular any of the aforementioned most preferred embodiments, is used in a cleaning composition and / or a fabric care and home care product, preferably a cleaning composition for fabric care and home care, the cleaning composition being preferably a laundry detergent formulation or a dishwashing detergent formulation, optionally, preferably at least one enzyme chosen from one or more of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, mannanases and peroxidases, as well as combinations of at least two of the aforementioned types, preferably the at least one enzyme chosen from lipases, at least one grafted polymer is present in an amount ranging from about 0.01% to about 20%, preferably from about 0.05% to about 15%, more preferably from about 0.1% to about 10%, and most preferably from about 0.5% to about 5% by weight of the total composition or product; Such products or compositions further comprise from about 1% to about 70% by weight of a surfactant system.

[0275] In further most preferred embodiments, the laundry detergent, dishwashing composition, cleaning composition, or fabric care and home care product comprises at least one grafted polymer obtained by a process as detailed in any of the preceding most preferred embodiments, or as detailed in any of such embodiments disclosed herein, including any of the preceding most preferred embodiments that specifically disclose such a process.

[0276] In a further most preferred embodiment, the graft polymer of or obtainable by any of the above most preferred embodiments is used as an ingredient in a composition or product which is a fabric care and home care product, a cleaning composition, an institutional and corporate cleaning product, more preferably a cleaning composition, most preferably a laundry detergent formulation, preferably using an enzyme selected from lipase, hydrolase, amylase, protease, cellulase, hemicellulase, phospholipase, esterase, pectinase, cutinase, deoxyribonuclease, xylanase, mannanase, dispersin, oxidoreductase, lactase, and peroxidase for the inhibition of dye transfer. and at least one enzyme selected from one or more of the above, as well as a combination of at least two of the aforementioned types, wherein the at least one grafted polymer is each present in such composition or product at a concentration of 0.05% to about 20%, preferably 0.05 to 10%, more preferably about 0.1% to 8%, even more preferably about 0.2% to about 6%, even more preferably about 0.2% to about 4%, and most preferably up to 2%, by weight percent based on the total weight of such composition or product, including all values ​​therebetween, and all ranges obtained by selecting any of the lower limits and combining them with any of the upper limits, each percentage being expressed as a weight percent based on the total weight of such composition or product.

[0277] In a further most preferred embodiment, the grafted polymer of or obtained by any of the embodiments disclosed herein, in particular any of the aforementioned most preferred embodiments, is used in such products or compositions further comprising from about 1% to about 70% by weight of a surfactant system.

[0278] In a further most preferred embodiment, the laundry detergent, cleaning composition, or fabric care and home care product comprises at least one grafted polymer of or obtained by any of the embodiments disclosed herein, in particular any of the aforementioned most preferred embodiments, or obtained by a process detailed in any of the embodiments disclosed herein, including in particular any of the aforementioned most preferred embodiments disclosing such a process.

[0279] In further most preferred embodiments, the compositions are included in the part of the invention that are fabric care and home care products, cleaning compositions, institutional and corporate cleaning products, cosmetics or personal care products, oil field formulations such as emulsion breakers for crude oil, pigment dispersions for inks such as inkjet inks, electroplating products, cementitious compositions, lacquers, paints, agrochemical formulations, preferably laundry detergents, dishwashing compositions, cleaning compositions, and / or fabric care and home care products, each containing at least one grafted polymer of or obtained by any of the embodiments disclosed herein, in particular any of the most preferred embodiments mentioned above.

[0280] In any of the embodiments of the present invention, particularly such laundry detergent, cleaning composition, or fabric care and home care product as detailed in the previous paragraph, the at least one grafted polymer - particularly as detailed in any of the embodiments disclosed herein, including any of the most preferred embodiments disclosed above that disclose such grafted polymers - is present in a concentration of from about 0.05% to about 10%, preferably from about 0.1% to 8%, more preferably from about 0.2% to about 6%, even more preferably from about 0.2% to about 4%, and most preferably up to 2%, by weight percent based on the total weight of such composition or product, including all values ​​therebetween, and all ranges obtained by selecting any of the lower limits and combining any of the upper limits, each expressed as a weight percent based on the total weight of such composition or product, and optionally further preferably an enzyme selected from the group consisting of lipase, hydrolase, amylase, protease, cellulase, hemicellulose, glyceryl esterase ... at least one enzyme selected from one or more of the following: lyase, phospholipase, esterase, pectinase, cutinase, deoxyribonuclease, xylanase, mannanase, dispersin, oxidoreductases, lactase, and peroxidase, as well as a combination of at least two of the foregoing types, and optionally an antimicrobial agent selected from the group consisting of 2-phenoxyethanol; preferably comprising said antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition, more preferably comprising 0.1 to 2% phenoxyethanol, and optionally 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, and further comprising a surfactant system constituting from about 1% to 70% by weight of such detergent, composition, or product.

[0281] In further embodiments, the present invention also encompasses compositions comprising a graft polymer and / or a polymer backbone, each as described herein above, and further comprising an antimicrobial agent, as disclosed hereinafter, 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 0.1 to 2% phenoxyethanol.

[0282] In a further embodiment, the present invention also encompasses a method of protecting an aqueous composition from microbial contamination or growth, such composition comprising a grafted polymer and / or a polymer backbone, respectively, as described herein above, 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 being preferably 2-phenoxyethanol.

[0283] 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 laundry softener composition, each of which comprises a grafted polymer and / or a polymer backbone as described herein above, and each of which further comprises 4,4'-dichloro 2-hydroxydiphenyl ether, at a concentration of from 0.001 to 3%, preferably from 0.002 to 1%, more preferably from 0.01 to 0.6%, by weight of the composition.

[0284] In a further embodiment, the present invention also encompasses a method of laundering a fabric or cleaning a hard surface, the method comprising treating the fabric or hard surface with a cleaning composition, more preferably with a liquid laundry detergent composition or a liquid hand dishwashing composition, even more preferably with a liquid laundry detergent composition or a liquid laundry softener composition, such compositions comprising a grafted polymer and / or a polymer backbone, each as described herein above, such compositions further comprising 4,4'-dichloro 2-hydroxydiphenyl ether.

[0285] The following examples will further illustrate the invention without limiting its scope. EXAMPLES

[0286] Polymer Measurements The K value is a measure of the relative viscosity of a diluted polymer solution and is a relative measure of the average molecular weight. As the average molecular weight of a particular polymer increases, the K value tends to increase. The K value is measured according to the method of H. Fikentscher in “Cellulosechemie”, 1932,13,58, at 23°C in a 3% by weight NaCl solution with a polymer concentration of 1% polymer.

[0287] The number average molecular weight (M n ), weight average molecular weight (M w ) and polydispersity M w / M n was measured in tetrahydrofuran by gel permeation chromatography. Tetrahydrofuran containing 0.035 mol / L diethanolamine was used as the mobile phase (eluent). The concentration of the graft polymer in tetrahydrofuran was 2.0 mg / mL. After filtering (pore size 0.2 μm), 100 μL of this solution was injected into the GPC system. Four different columns (heated to 60 °C) were used for separation (SDV precolumn, SDV 1000A, SDV 100000A, SDV 1000000A). The GPC system was operated at a flow rate of 1 mL / min. A DRI Agilent 1100 was used as the detection system. The molecular weight M was used for calibration. n Poly(ethylene glycol) (PEG) standards (PL) with concentrations ranging from 106 to 1 378 000 g / mol were used.

[0288] Methods for measuring the biodegradability of polymers Biodegradation in wastewater was tested in triplicate using the OECD 301F manometric respirometry method. 30 mg / mL of the test substance is inoculated into wastewater taken from the Mannheim Wastewater Treatment Plant and incubated in closed flasks at 25°C for 28 days. The oxygen consumed during this period is measured as the pressure change in the flask using an OxiTop C (WTW). The evolved CO2 is absorbed using a NaOH solution. The amount of oxygen consumed by the microbial population during the biodegradation of the test substance is expressed as % of ThOD (theoretical oxygen demand) after correction with a blank.

[0289] The procedures set forth below were carried out using the materials and ratios and amounts further set forth in Tables 1 and 2.

[0290] Other inventive and comparative graft polymers can be synthesized following these procedures by adjusting the type and molecular weight and composition of the polymer backbone, as well as the amount and type of monomer for grafting thereto.

[0291] Example 1: Graft polymerization of vinyl acetate (20 wt%) onto EO / PO backbone (Mn 2500 g / mol; 60% EO; 80 wt%) In a nitrogen atmosphere, 480 g of an EO / PO statistical copolymer was first charged into a polymerization vessel equipped with a stirrer and a reflux condenser, and melted at 90°C.

[0292] Feed 1, consisting of 2.99 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 25.73 g of tripropylene glycol, was dosed into the stirred tank over 6 hours and 10 minutes at 90° C. 5.56% of Feed 1 was dosed in the first 10 minutes, and the remainder was dosed at a constant feed rate over 6 hours. 10 minutes after Feed 1 was started, Feed 2 (120 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate over 6 hours at 90° C. Once the feed was complete, Feed 3, consisting of 1.89 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 16.27 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90° C. Once the feed addition was complete, the mixture was stirred at 90° C. for 1 hour.

[0293] Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0294] Example 2: Graft polymerization of vinyl acetate (30 wt%) onto EO / PO backbone (Mn 2500 g / mol; 60% EO; 70 wt%) In a nitrogen atmosphere, 420 g of an EO / PO statistical copolymer was first charged into a polymerization vessel equipped with a stirrer and a reflux condenser, and melted at 90°C.

[0295] Feed 1, consisting of 2.99 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 25.73 g of tripropylene glycol, was dosed into the stirred tank over 6 hours and 10 minutes at 90° C. 5.56% of Feed 1 was dosed in the first 10 minutes, and the remainder was dosed at a constant feed rate over 6 hours. 10 minutes after Feed 1 was started, Feed 2 (180 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate over 6 hours at 90° C. Once the feed was complete, Feed 3, consisting of 1.89 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 16.27 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90° C. Once the feed addition was complete, the mixture was stirred at 90° C. for 1 hour.

[0296] Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0297] Example 3: Graft polymerization of vinyl acetate (40 wt%) onto EO / PO backbone (Mn 2500 g / mol; 60% EO; 60 wt%) First, 600 g of an EO / PO statistical copolymer was placed in a polymerization vessel equipped with a stirrer and a reflux condenser in a nitrogen atmosphere and melted at 90°C.

[0298] Feed 1, consisting of 4.02 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 35.38 g of tripropylene glycol, was dosed into the stirred tank at 90° C. over a period of 6 hours and 10 minutes. 5.56% of Feed 1 was dosed in the first 10 minutes, and the remainder was dosed at a constant feed rate over 6 hours. 10 minutes after Feed 1 was started, Feed 2 (400 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate over 6 hours at 90° C. Once the feed was complete, Feed 3, consisting of 2.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.44 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90° C. Once the addition of the feed was complete, the mixture was stirred at 90° C. for 1 hour.

[0299] Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0300] Example 4: Graft polymerization of vinyl acetate (50 wt%) onto EO / PO backbone (Mn 2500 g / mol; 60% EO; 50 wt%) First, 500 g of an EO / PO statistical copolymer was placed in a polymerization vessel equipped with a stirrer and a reflux condenser in a nitrogen atmosphere and melted at 90°C.

[0301] Feed 1, consisting of 3.98 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 41.91 g of tripropylene glycol, was dosed into the stirred tank over 6 hours and 10 minutes at 90° C. 5.56% of Feed 1 was dosed in the first 10 minutes, and the remainder was dosed at a constant feed rate over 6 hours. 10 minutes after Feed 1 was started, Feed 2 (500 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate over 6 hours at 90° C. Once the feed was complete, Feed 3, consisting of 2.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 26.85 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90° C. Once the feed addition was complete, the mixture was stirred at 90° C. for 1 hour.

[0302] Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0303] Example 5: Graft polymerization of vinyl acetate (70 wt%) onto EO / PO backbone (Mn 2500 g / mol; 60% EO; 30 wt%) First, 300 g of an EO / PO statistical copolymer was placed in a polymerization vessel equipped with a stirrer and a reflux condenser in a nitrogen atmosphere and melted at 90°C.

[0304] Feed 1, consisting of 3.98 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 41.91 g of 1,2-propanediol, was dosed into the stirred tank over 6 hours and 10 minutes at 90° C. 5.56% of Feed 1 was dosed in the first 10 minutes, and the remainder was dosed at a constant feed rate over 6 hours. 10 minutes after Feed 1 was started, Feed 2 (700 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate over 6 hours at 90° C. Once the feed was complete, Feed 3, consisting of 2.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 26.85 g of 1,2-propanediol, was dosed at a constant flow rate within 56 minutes at 90° C. Once the feed addition was complete, the mixture was stirred at 90° C. for 1 hour.

[0305] Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0306] Example 6: Graft polymerization of vinyl acetate (40 wt%) onto EO / PO backbone B1 (Mn 2500 g / mol; 90% EO; 60 wt%) In a nitrogen atmosphere, 420 g of an EO / PO statistical copolymer was first charged into a polymerization vessel equipped with a stirrer and a reflux condenser, and melted at 90°C.

[0307] Feed 1, consisting of 3.05 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 30.02 g of tripropylene glycol, was dosed into the stirred tank over 6 hours and 10 minutes at 90° C. 5.56% of Feed 1 was dosed in the first 10 minutes, and the remainder was dosed at a constant feed rate over 6 hours. 10 minutes after Feed 1 was started, Feed 2 (280 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate over 6 hours at 90° C. Once the feed was complete, Feed 3, consisting of 1.93 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 18.98 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90° C. Once the feed addition was complete, the mixture was stirred at 90° C. for 1 hour.

[0308] Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0309] Example 7: Graft polymerization of vinyl acetate (40 wt%) onto EO / PO backbone B2 (Mn 2500 g / mol; 75% EO; 60 wt%) In a nitrogen atmosphere, 420 g of an EO / PO statistical copolymer was first charged into a polymerization vessel equipped with a stirrer and a reflux condenser, and melted at 90°C.

[0310] Feed 1, consisting of 3.49 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 30.02 g of tripropylene glycol, was dosed into the stirred tank over 6 hours and 10 minutes at 90° C. 5.56% of Feed 1 was dosed in the first 10 minutes, and the remainder was dosed at a constant feed rate over 6 hours. 10 minutes after Feed 1 was started, Feed 2 (280 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate over 6 hours at 90° C. Once the feed was complete, Feed 3, consisting of 2.20 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 18.98 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90° C. Once the addition of the feed was complete, the mixture was stirred at 90° C. for 1 hour.

[0311] Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0312] Example 8: Graft polymerization of vinyl acetate (40 wt%) onto EO / PO backbone B3 (Mn 2500 g / mol; 55% EO; 60 wt%) In a nitrogen atmosphere, 420 g of an EO / PO statistical copolymer was first charged into a polymerization vessel equipped with a stirrer and a reflux condenser, and melted at 90°C.

[0313] Feed 1, consisting of 3.70 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 30.02 g of tripropylene glycol, was dosed into the stirred tank at 90° C. over a period of 6 hours and 10 minutes. 5.56% of Feed 1 was dosed in the first 10 minutes, and the remainder was dosed at a constant feed rate over 6 hours. 10 minutes after Feed 1 was started, Feed 2 (280 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate over 6 hours at 90° C. Once the feed was complete, Feed 3, consisting of 2.34 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 18.98 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90° C. Once the addition of the feed was complete, the mixture was stirred at 90° C. for 1 hour.

[0314] Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0315] Example 9: Graft polymerization of vinyl acetate (40 wt%) onto EO / PO backbone B4 (Mn 2500 g / mol; 35% EO; 60 wt%) In a nitrogen atmosphere, 480 g of an EO / PO statistical copolymer was first charged into a polymerization vessel equipped with a stirrer and a reflux condenser, and melted at 90°C.

[0316] Feed 1, consisting of 4.48 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 34.30 g of tripropylene glycol, was dosed into the stirred tank over 6 hours and 10 minutes at 90° C. 5.56% of Feed 1 was dosed in the first 10 minutes, and the remainder was dosed at a constant feed rate over 6 hours. 10 minutes after Feed 1 was started, Feed 2 (320 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate over 6 hours at 90° C. Once the feed was complete, Feed 3, consisting of 2.83 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 21.69 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90° C. Once the feed addition was complete, the mixture was stirred at 90° C. for 1 hour.

[0317] Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0318] Example 10: Graft polymerization of vinyl acetate (40 wt%) onto EO / PO backbone B5 (Mn 2500 g / mol; 20% EO; 60 wt%) In a nitrogen atmosphere, 420 g of an EO / PO statistical copolymer was first charged into a polymerization vessel equipped with a stirrer and a reflux condenser, and melted at 90°C.

[0319] Feed 1, consisting of 4.36 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 30.02 g of tripropylene glycol, was dosed into the stirred tank over 6 hours and 10 minutes at 90° C. 5.56% of Feed 1 was dosed in the first 10 minutes, and the remainder was dosed at a constant feed rate over 6 hours. 10 minutes after Feed 1 was started, Feed 2 (280 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate over 6 hours at 90° C. Once the feed was complete, Feed 3, consisting of 2.75 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 18.98 g of tripropylene glycol, was dosed at a constant rate within 56 minutes at 90° C. Once the feed addition was complete, the mixture was stirred at 90° C. for 1 hour.

[0320] Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0321] Example 11: Graft polymerization of vinyl acetate (40 wt%) onto EO / PO backbone (Mn2 300 g / mol; 50% EO; 60 wt%) First, 600 g of an EO / PO statistical copolymer was placed in a polymerization vessel equipped with a stirrer and a reflux condenser in a nitrogen atmosphere and melted at 90°C.

[0322] Feed 1, consisting of 4.02 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 35.38 g of 1,2-propanediol, was dosed into the stirred tank over 6 hours and 10 minutes at 90° C. 5.56% of Feed 1 was dosed in the first 10 minutes, and the remainder was dosed at a constant feed rate over 6 hours. 10 minutes after Feed 1 was started, Feed 2 (400 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate over 6 hours at 90° C. Once the feed was complete, Feed 3, consisting of 2.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.44 g of 1,2-propanediol, was dosed at a constant rate within 56 minutes at 90° C. Once the feed addition was complete, the mixture was stirred at 90° C. for 1 hour.

[0323] Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0324] Example 12: Graft polymerization of vinyl acetate (40 wt%) onto EO / PO backbone (Mn 3000 g / mol; 60% EO; 60 wt%) First, 600 g of an EO / PO statistical copolymer was placed in a polymerization vessel equipped with a stirrer and a reflux condenser in a nitrogen atmosphere and melted at 90°C.

[0325] Feed 1, consisting of 4.02 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 35.38 g of 1,2-propanediol, was dosed into the stirred tank over 6 hours and 10 minutes at 90° C. 5.56% of Feed 1 was dosed in the first 10 minutes, and the remainder was dosed at a constant feed rate over 6 hours. 10 minutes after Feed 1 was started, Feed 2 (400 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate over 6 hours at 90° C. Once the feed was complete, Feed 3, consisting of 2.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.44 g of 1,2-propanediol, was dosed at a constant rate within 56 minutes at 90° C. Once the feed addition was complete, the mixture was stirred at 90° C. for 1 hour.

[0326] Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0327] Example 13: Graft polymerization of vinyl acetate (20 wt%) onto EO / PO backbone (Mn 4100 g / mol; 60% EO; 80 wt%) A 4 liter vessel equipped with a stirrer and three feeds was charged with 1000 g of EO / PO statistical copolymer, heated to 90° C. and purged with nitrogen. A solution of radical initiator (56 g; mixture of tert-butylperoxy-2-ethylhexanoat in n-butyl acetate; 23.8% by weight) was fed through feed 1 over 7 hours. 15 minutes after the start of feed 1, an amount of 250 g of vinyl acetate was fed continuously through feed 2 within 6 hours. Once feed 2 was complete, the reaction mixture was stirred at 90° C. for 2 hours. Then feed 3 (2 hours, solution of 44 g of radical initiator mixture) was started. Once feed 3 was complete, the reaction mixture was stirred at 90° C. for another 2 hours. The pressure was then set to 10 mbar and the volatile components were removed with stirring at 100° C. and 10 mbar, then cooled to ambient temperature with stirring. The inventive graft polymer mixture was obtained as a clear liquid, 1270 g.

[0328] Example 14: Graft polymerization of vinyl acetate (20 wt%) onto EO / PO main chain (Mn 6400 g / mol; 60% EO; 80 wt%) A 4 liter vessel equipped with a stirrer and three feeds was charged with 1000 g of EO / PO statistical copolymer, heated to 90° C. and purged with nitrogen. A solution of radical initiator (56 g; mixture of tert-butylperoxy-2-ethylhexanoat in n-butyl acetate; 23.8% by weight) was fed through feed 1 over 7 hours. 15 minutes after the start of feed 1, an amount of 250 g of vinyl acetate was fed continuously through feed 2 within 6 hours. Once feed 2 was complete, the reaction mixture was stirred at 90° C. for 2 hours. Then feed 3 (2 hours, solution of 44 g of radical initiator mixture) was started. Once feed 3 was complete, the reaction mixture was stirred at 90° C. for another 2 hours. The pressure was then set to 10 mbar and the volatile components were removed with stirring at 100° C. and 10 mbar, then cooled to ambient temperature with stirring. The inventive graft polymer mixture was obtained as a clear liquid, 1250 g.

[0329] Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0330] Example 15: Graft polymerization of vinyl acetate (40% by weight) onto a glycerin-containing polyalkoxylate backbone (Mn 3550 g / mol; 60% by weight) Ex.15a: Main chain: The backbone was prepared starting with glycerin and KOH, which were dried in vacuum to remove residual water. The glycerin was then reacted first with ethylene oxide, then with a mixture of ethylene oxide and propylene oxide to obtain a statistical copolymer block, and then ethylene oxide was used again to obtain a polymer with the following structure: Glycerin[2,25]-PO[5,54]-PO[19,72] / EO[67,49]-EO[5,0], The numbers in brackets are the molar amounts of the individual moieties.

[0331] Water and acid (glacial acetic acid) were then added (in equimolar amounts), the water was removed and the crystallized potassium salt was removed by filtration. (Mn 3550 g / mol) (Commercially available as Lupranol® 2048)

[0332] Ex.15b: Graft polymer In a nitrogen atmosphere, a polymerization vessel equipped with a stirrer and reflux condenser was first charged with 600 g of Ex.15a backbone (Mn 3550 g / mol) and melted at 90°C. Feed 1, consisting of 5.60 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 42.88 g of tripropylene glycol, was charged to the stirred vessel over 6 hours and 10 minutes at 90°C. 5.56 wt% of Feed 1 was charged in the first 10 minutes, and the remainder was charged at a constant feed rate over 6 hours. 10 minutes after the start of Feed 1, Feed 2 (400 g of vinyl acetate) was started and charged to the reactor at a constant feed rate over 6 hours at 90°C. Once the feed was completed, Feed 3, consisting of 3.54 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 27.11 g of tripropylene glycol, was fed at a constant flow rate within 56 minutes at 90°C. Once the feed addition was complete, the mixture was stirred for 1 h at 90° C. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0333] Example 16: Graft polymerization of vinyl acetate (40 wt%) onto a diethylene glycol-containing polyalkoxylate backbone (Mn2 200 g / mol; 60 wt%) Ex.16a: Main chain: The backbones were prepared starting with diethylene glycol and KOH, which were dried in vacuum to remove residual water. Diethylene glycol (DEG) was then reacted first with ethylene oxide, then with a mixture of ethylene oxide and propylene oxide to obtain a statistical copolymer block, then ethylene oxide was used again to obtain a polymer with the following structure: DEG[4,9]-EO[12,4]-PO[20,9] / EO[47,5]-EO[14,3], The numbers in brackets are the molar amounts of the individual moieties.

[0334] Water and acid (glacial acetic acid) were then added (in equimolar amounts), the water was removed and the crystallized potassium salt was removed by filtration. (Mn 2200 g / mol). (Commercially available as Lupranol® 6000 / 1)

[0335] Ex.16b: Graft polymer In a polymerization vessel equipped with a stirrer and reflux condenser under nitrogen, 600 g of the backbone of Ex.16a was first charged and melted at 90°C. Feed 1, consisting of 3.36 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 25.73 g of tripropylene glycol, was charged to the stirred vessel over 6 hours and 10 minutes at 90°C. 5.56 wt% of Feed 1 was charged in the first 10 minutes, and the remainder was charged at a constant feed rate over 6 hours. 10 minutes after the start of Feed 1, Feed 2 (240 g of vinyl acetate) was started and charged to the reactor at a constant feed rate over 6 hours at 90°C. Once the feed was completed, Feed 3, consisting of 2.12 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 16.27 g of tripropylene glycol, was fed at a constant flow rate within 56 minutes at 90°C. Once the addition of the feed was complete, the mixture was stirred at 90°C for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0336] Synthesis procedure for main chains B1 to B5 Main chain B1: Random copolymer of ethylene oxide and propylene oxide with 90% by weight of EO, molecular weight 2500 g / mol

[0337] Backbone B1a: diethylene glycol ethoxylated with 14.4 moles of ethylene oxide and propoxylated with 1.26 moles of propylene oxide (random). In a 2 L autoclave, 106.1 g of diethylene glycol and 1.63 g of potassium tert-butylate were mixed. The autoclave was purged with nitrogen three times and heated to 140° C. A mixture of 634.4 g of ethylene oxide and 73.2 g of propylene oxide was added within 13 hours. The mixture was stirred at 140° C. for another 5 hours to complete the reaction. The reaction mixture was stripped with nitrogen and volatile compounds were removed under vacuum at 80° C. After filtration, 815.0 g of light brown wax was obtained. 1H-NMR confirmed the expected structure.

[0338] Main chain B1b: Random copolymer of ethylene oxide and propylene oxide with 90% by weight of ethylene oxide, molecular weight Mn=2500 g / mol (Diethylene glycol ethoxylated with 48.0 moles of ethylene oxide and propoxylated with 4.2 moles of propylene oxide (random)) In a 2 L autoclave, 366.1 g of diethylene glycol ethoxylated with 14.4 moles of ethylene oxide and propoxylated with 1.26 moles of propylene oxide (random, example 1a) and 1.49 g of potassium tert-butylate were mixed. The autoclave was purged with nitrogen three times and heated to 140° C. A mixture of 661.1 g of ethylene oxide and 76.8 g of propylene oxide was added within 15 hours. The mixture was stirred at 140° C. for another 5 hours to complete the reaction. The reaction mixture was stripped with nitrogen and volatile compounds were removed under vacuum at 80° C. After filtration, 1105.0 g of light brown wax was obtained. 100% of ethylene oxide in CDCl3 was added at 140° C. and 100% of propylene ... 1 H-NMR confirmed the expected structure.

[0339] Main chain B2: Random copolymer of ethylene oxide and propylene oxide with 75% by weight of ethylene oxide, molecular weight Mn=2500 g / mol

[0340] Backbone B2a: Diethylene glycol ethoxylated with 12.1 moles of ethylene oxide and propoxylated with 3.2 moles of propylene oxide (random). In a 2 L autoclave, 106.1 g of diethylene glycol and 1.65 g of potassium tert-butylate were mixed. The autoclave was purged with nitrogen three times and heated to 140° C. A mixture of 532.6 g of ethylene oxide and 186.4 g of propylene oxide was added within 13 hours. The mixture was stirred at 140° C. for another 5 hours to complete the reaction. The reaction mixture was stripped with nitrogen and volatile compounds were removed under vacuum at 80° C. After filtration, 825.0 g of light brown oil was obtained. 1 H-NMR confirmed the expected structure.

[0341] Main chain B2b: Random copolymer of ethylene oxide and propylene oxide with 75% by weight of ethylene oxide, molecular weight Mn=2500 g / mol (Diethylene glycol ethoxylated with 40.3 moles of ethylene oxide and propoxylated with 10.7 moles of propylene oxide (random)) In a 2 L autoclave, 370.1 g of diethylene glycol ethoxylated with 12.1 moles of ethylene oxide and propoxylated with 3.2 moles of propylene oxide (random, example 2a) and 1.50 g of potassium tert-butylate were mixed. The autoclave was purged with nitrogen three times and heated to 140° C. A mixture of 559.2 g of ethylene oxide and 195.8 g of propylene oxide was added within 15 hours. The mixture was stirred at 140° C. for another 5 hours to complete the reaction. The reaction mixture was stripped with nitrogen and volatile compounds were removed under vacuum at 80° C. After filtration, 1130.0 g of a light brown oil was obtained. 100% of ethylene oxide in CDCl3 was added at 140° C. and 100% of propylene ... 1 H-NMR confirmed the expected structure.

[0342] Main chain B3: Random copolymer of ethylene oxide and propylene oxide with 55% by weight of ethylene oxide, molecular weight Mn=2500 g / mol

[0343] Backbone B3a Diethylene glycol ethoxylated with 8.7 moles of ethylene oxide and propoxylated with 5.8 moles of propylene oxide (random). In a 2 L autoclave, 106.1 g of diethylene glycol and 1.65 g of potassium tert-butylate were mixed. The autoclave was purged with nitrogen three times and heated to 140° C. A mixture of 381.9 g of ethylene oxide and 334.5 g of propylene oxide was added within 13 hours. The mixture was stirred at 140° C. for another 5 hours to complete the reaction. The reaction mixture was stripped with nitrogen and volatile compounds were removed under vacuum at 80° C. After filtration, 822.0 g of a light brown oil was obtained. 1 H-NMR confirmed the expected structure.

[0344] Main chain B3b: Random copolymer of ethylene oxide and propylene oxide with 55% by weight of ethylene oxide, molecular weight Mn=2500 g / mol (Diethylene glycol ethoxylated with 28.9 moles of ethylene oxide and propoxylated with 19.2 moles of propylene oxide (random)) In a 2 L autoclave, 370.1 g of diethylene glycol ethoxylated with 8.7 moles of ethylene oxide and propoxylated with 5.8 moles of propylene oxide (random, example 3a) and 1.50 g of potassium tert-butylate were mixed. The autoclave was purged with nitrogen three times and heated to 140° C. A mixture of 370.2 g of ethylene oxide and 351.6 g of propylene oxide was added within 15 hours. The mixture was stirred at 140° C. for another 5 hours to complete the reaction. The reaction mixture was stripped with nitrogen and volatile compounds were removed under vacuum at 80° C. After filtration, 1128.0 g of a light brown oil was obtained. 100% ethylene oxide in CDCl3 was added at 140° C. for 15 hours. The mixture was stirred ... 1 H-NMR confirmed the expected structure.

[0345] Main chain B4: Random copolymer of ethylene oxide and propylene oxide with 35% by weight of ethylene oxide, molecular weight Mn=2500 g / mol

[0346] Backbone B4a: Diethylene glycol ethoxylated with 5.3 moles of ethylene oxide and propoxylated with 8.3 moles of propylene oxide (random). In a 2 L autoclave, 106.1 g of diethylene glycol and 1.65 g of potassium tert-butylate were mixed. The autoclave was purged with nitrogen three times and heated to 140° C. A mixture of 233.9 g of ethylene oxide and 482.6 g of propylene oxide was added within 13 hours. The mixture was stirred at 140° C. for another 5 hours to complete the reaction. The reaction mixture was stripped with nitrogen and volatile compounds were removed under vacuum at 80° C. After filtration, 820.0 g of light brown oil was obtained. 1 H-NMR confirmed the expected structure.

[0347] Main chain B4b: Random copolymer of ethylene oxide and propylene oxide with 35% by weight of ethylene oxide, molecular weight Mn=2500 g / mol (Diethylene glycol ethoxylated with 17.7 moles of ethylene oxide and propoxylated with 27.7 moles of propylene oxide (random)) In a 2L autoclave, 370.2 g of diethylene glycol ethoxylated with 5.3 moles of ethylene oxide and propoxylated with 8.3 moles of propylene oxide (random, Example 4a) and 1.51 g of potassium tert-butylate were mixed. The autoclave was purged with nitrogen three times and heated to 140°C. A mixture of 245.6 g of ethylene oxide and 506.7 g of propylene oxide was added within 15 hours. The mixture was stirred at 140°C for another 5 hours to complete the reaction. The reaction mixture was stripped with nitrogen and volatile compounds were removed under vacuum at 80°C. After filtration, 1119.0 g of a light brown oil was obtained. 100% ethylene oxide in CDCl3 was added at 140°C. 100% ethylene oxide in CDCl3 was added at 140°C. 100% ethylene oxide in CDCl3 was added at 140°C. 100% propylene ... 1 H-NMR confirmed the expected structure.

[0348] Main chain B5: Random copolymer of ethylene oxide and propylene oxide with 20% by weight of ethylene oxide, molecular weight Mn=2500 g / mol

[0349] Backbone B5a: Diethylene glycol ethoxylated with 2.8 moles of ethylene oxide and propoxylated with 10.3 moles of propylene oxide (random). In a 2 L autoclave, 106.1 g of diethylene glycol and 1.65 g of potassium tert-butylate were mixed. The autoclave was purged with nitrogen three times and heated to 140° C. A mixture of 122.9 g of ethylene oxide and 595.9 g of propylene oxide was added within 13 hours. The mixture was stirred at 140° C. for another 5 hours to complete the reaction. The reaction mixture was stripped with nitrogen and volatile compounds were removed under vacuum at 80° C. After filtration, 821.0 g of light brown oil was obtained. 1 H-NMR confirmed the expected structure.

[0350] Main chain B5b: Random copolymer of ethylene oxide and propylene oxide with 20% by weight of ethylene oxide, molecular weight Mn=2500 g / mol (Diethylene glycol ethoxylated with 9.3 moles of ethylene oxide and propoxylated with 34.2 moles of propylene oxide (random)) In a 2 L autoclave, 371.2 g of diethylene glycol ethoxylated with 2.8 moles of ethylene oxide and propoxylated with 10.3 moles of propylene oxide (random, Example 5a) and 1.51 g of potassium tert-butylate were mixed. The autoclave was purged with nitrogen three times and heated to 140° C. A mixture of 129.0 g of ethylene oxide and 625.7 g of propylene oxide was added within 15 hours. The mixture was stirred at 140° C. for another 5 hours to complete the reaction. The reaction mixture was stripped with nitrogen and volatile compounds were removed under vacuum at 80° C. After filtration, 1135.0 g of a light brown oil was obtained. 100% ethylene oxide in CDCl3 was added at 140° C. for 15 hours. The mixture was stirred ... 1 H-NMR confirmed the expected structure.

[0351] Synthesis procedures for comparative examples: Comp.Ex.1: Graft polymerization of vinyl acetate (10 wt%) onto EO / PO main chain (Mn2500g / mol; 60% EO; 90 wt%) In a nitrogen atmosphere, 900 g of an EO / PO statistical copolymer was first charged into a polymerization vessel equipped with a stirrer and a reflux condenser, and melted at 90°C.

[0352] Feed 1, consisting of 4.02 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 35.38 g of 1,2-propanediol, was dosed into the stirred tank over 6 hours and 10 minutes at 90° C. 5.56% of Feed 1 was dosed in the first 10 minutes, and the remainder was dosed at a constant feed rate over 6 hours. 10 minutes after Feed 1 was started, Feed 2 (100 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate over 6 hours at 90° C. Once the feed was complete, Feed 3, consisting of 2.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.44 g of 1,2-propanediol, was dosed at a constant rate within 56 minutes at 90° C. Once the addition of the feed was complete, the mixture was stirred at 90° C. for 1 hour.

[0353] Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 h.

[0354] Comp.Ex.2: Graft polymerization of vinyl acetate (80% by weight) onto EO / PO main chain (Mn2500g / mol; 60% EO; 20% by weight) In a nitrogen atmosphere, 200 g of an EO / PO statistical copolymer was first charged into a polymerization vessel equipped with a stirrer and a reflux condenser, and melted at 90°C.

[0355] Feed 1, consisting of 4.02 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 35.38 g of 1,2-propanediol, was dosed into the stirred tank over 6 hours and 10 minutes at 90° C. 5.56% of Feed 1 was dosed in the first 10 minutes, and the remainder was dosed at a constant feed rate over 6 hours. 10 minutes after Feed 1 was started, Feed 2 (800 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate over 6 hours at 90° C. Once the feed was complete, Feed 3, consisting of 2.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.44 g of 1,2-propanediol, was dosed at a constant rate within 56 minutes at 90° C. Once the addition of the feed was complete, the mixture was stirred at 90° C. for 1 hour.

[0356] [Table 8]

[0357] [Table 9]

[0358] [Table 10]

[0359] The cloud points of some of the inventive polymers are shown below in Table 3. The inventive polymers exhibit lower cloud points by increasing the PO content in the backbone.

[0360] [Table 11]

[0361] Graft polymer application test Whiteness and cleaning performance of polymers in liquid detergents. The following water soluble single dose (SUD) detergent compositions A and B are prepared by traditional means known to those skilled in the art by mixing the listed ingredients (Table 4).

[0362] The whiteness maintenance of the polymers of the present invention is evaluated according to the method for evaluating the whiteness performance of polymers by directly comparing the whiteness performance of the reference composition A and the test composition B. The ΔWI(CIE) of composition A versus composition B is reported in Table 6 as an indication of the whiteness performance merit of the polymer.

[0363] [Table 12]

[0364] Methods for evaluating whiteness maintenance performance in detergents Test preparation: For the whiteness benefit test the following fabrics are provided: NA polyester: PW19, available from Empirical Manufacturing Company, Cincinnati, OH, USA Knitted Cotton 1: Test fabric, Inc403 cotton interlock knit tubular CW120, available from Empirical Manufacturing Company, Cincinnati, OH, USA Polycotton

[0365] The "washed and FE treated" fabrics were prepared according to the following method: 400 g of fabric was washed twice at 60°C with 18.6 g of Ariel™ compact powder detergent in a WE Miniwasher (3.5 liters of water) using a short program (45 min wash cycle followed by 3 rinse cycles; total program 90 min) and 2 short programs at 60°C without detergent, followed by 3 short programs at 40°C with 8.2 g of Lenor™ concentrate (fiber strengthener) added to each main load. The fabrics were then tumble dried on heavy duty until dry.

[0366] "Washed" fabrics were prepared according to the following method: 400 g of fabric was washed twice at 60° C. with 18.6 g of Ariel™ compact powder detergent in a WE Miniwasher (3.5 liters of water) using a short program (45 minute wash cycle followed by 3 rinse cycles; total program 90 minutes) and twice using a short program without detergent at 60° C. The fabric was then tumble dried on heavy duty until dry.

[0367] Test Method: Four fabric samples are prepared: polycotton, washed; knitted cotton, washed; NA polyester, washed and FE treated; knitted washed and FE treated.

[0368] Each sample was run in a 96-well plate simulated wash system that uses magnetized bearings to simulate the agitation of a typical full-scale washing machine according to the following conditions: 750 ppm detergent concentrate, 150 μL water per well, 25°C, 2.5 mM water hardness (2:1 Ca+2:Mg+2 molar ratio), pH 8.3 wash, 3000 ppm Arizona test dust (PTI, supplied by Powder Technology Inc).

[0369] Each polymer listed in Tables 5 / 6 is added at 15 ppm in the wash solution. Each fabric is washed for 60 minutes and dried in the dark under ambient conditions. For each wash condition, there are two 96-well plates with eight internal replicates per 96-well plate for a total of 16 replicates per wash condition.

[0370] Once the samples were dried, a Spectrolino imaging system (Gretag Macbeth, Spectro Scan 3.273) was used to image the L100 at each spot of the 96-well plate. * , a * , b *, and CIE WI are measured. For each treatment, the average CIE WI is determined. The delta CIE WI reported in the table below is the difference between the average CIE WI of the sample and the average CIE WI of a control sample that does not contain the test polymer.

[0371] The whiteness index (WI-index) determined for several different textile materials (see table below) was calculated as follows:

[0372] For the whiteness index, the CIE whiteness index formula was used and delta WI was calculated as follows: delta WI on substrate=WI technology-no WI.

[0373] "Equivalent Scaling Index" (for the examples listed) = (Sum (all WI fabrics tested with technology A) x 100) / Sum (all WI fabrics tested without technology), where the comparison is set to "100" for tests without grafted polymer.

[0374] [Table 13]

[0375] [Table 14]

Claims

1. (A) a copolymer backbone as a graft substrate, said copolymer backbone (A) being obtainable by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentene oxide, or 2,3-pentene oxide; a. the distribution of the alkylene oxide moieties within the copolymer backbone is in random order; b. a copolymer backbone having a molecular weight Mn (g / mol) in the range of 500 to 7000, preferably 6000 or less, more preferably 5000 or less, even more preferably 4500 or less, even more preferably 4000 or less, even more preferably 3500 or less, even more preferably 3000 or less, and most preferably 2500, preferably at least 1000, more preferably at least 1200; (B) polymeric side chains grafted onto said copolymer backbone, said polymeric side chains (B) being obtainable by polymerization of at least one vinyl ester monomer (B1) and optionally at least one other monomer (B2), and—if present—the weight ratio of monomer (B2) to monomer (B1) is less than 0.5, preferably less than 0.4, more preferably less than 0.3, even more preferably less than 0.2 and most preferably less than 0.1; A graft polymer comprising: In weight percent based on the total weight of the graft polymer, 25 to 85%, preferably 30 to 80%, more preferably 35 to 80%, even more preferably 40 to 75%, and most preferably 55 to 75% of said copolymer backbone (A); and 15 to 75%, preferably 20 to 70%, more preferably 20 to 65%, even more preferably 25 to 60%, and most preferably 25 to 45% of said polymer side chains (B).

2. The copolymer backbone (A) is i) obtainable by polymerization of at least two monomers selected from the group consisting of ethylene oxide, 1,2-propylene oxide, or 1,2-butylene oxide, preferably at least ethylene oxide being selected as one of the monomers, more preferably ethylene oxide and propylene oxide being selected as the only monomers; and / or ii) the relative amount of EO in said polymer backbone A is in the range of 5 to 95%, preferably 10 to 90%, more preferably 15 to 85%, and even more preferably at least 20 to 80% (all expressed as weight percent relative to the total mass of alkylene oxide in said polymer backbone (A)); and / or iii) The graft polymer according to claim 1, wherein essentially no monomer (B2) is used in the polymerization to obtain the side chain (B).

3. i) the graft polymer has a polydispersity Mw / Mn of <5, preferably <3.5, more preferably <3, most preferably in the range of 1.0 to 2.5 (Mw = weight average molecular weight, Mn = number average molecular weight [g / mol / g / mol]), ii) the copolymer backbone (A) is optionally end-capped with one or both end groups, preferably the copolymer backbone (A) is not end-capped with both end groups, or if the copolymer backbone (A) is end-capped, the end-capping is carried out with a C1-C25-alkyl group, preferably a C1-C4 group; iii) said polymer side chains (B) are obtained by radical polymerization of said at least one vinyl ester monomer (B1) and optionally at least one other monomer (B2) in the presence of said polymer backbone A, The graft polymer according to claim 1, which satisfies at least one of the following: Preferably, at least 10 wt. % of the total weight of vinyl ester monomers (B1) are selected from vinyl acetate, vinyl propionate, and vinyl laurate, more preferably vinyl acetate and vinyl laurate, most preferably vinyl acetate, the remaining amount of vinyl esters can be any other known vinyl ester, preferably at least 60, more preferably at least 70, even more preferably at least 80, even more preferably 90 wt. % vinyl acetate, most preferably essentially only vinyl acetate (i.e. about 100 wt. % or even 100 wt. % vinyl acetate) is used as vinyl ester (wt. % based on the total weight of vinyl ester monomers B1 used), Preferably, essentially no monomer (B2) is used in the graft polymer.

4. (A) 55 to 75% by weight (based on the total weight of the graft polymer) of the copolymer backbone (A) obtainable by polymerization of ethylene oxide and 1,2-propylene oxide as alkylene oxide monomers, wherein the alkylene oxide monomer distribution in the backbone is in random order, the molecular weight Mn (g / mol) of the copolymer backbone is in the range of 1200 to 2500, and the relative amount of EO in the polymer backbone (A) is 20 to 80% (by weight based on the total mass of alkylene oxides in the polymer backbone (A)); and (B) 25 to 45 weight percent (based on the total weight of the graft polymer) of the polymeric side chains grafted onto the copolymer backbone derived from vinyl acetate as the sole vinyl ester monomer (B1), essentially without any monomer (B2).

5. 2. The graft polymer of claim 1, wherein the biodegradability of the graft polymer is at least 30, preferably at least 35, and even more preferably at least 40%, within 28 days when tested according to OECD 301F.

6. 1. A method for producing a vinyl ester copolymer comprising polymerizing at least one vinyl ester monomer (B1) and optionally at least one further monomer (B2) in the presence of at least one copolymer backbone (A), a free-radical-forming initiator (C), and optionally up to 50% by weight of at least one organic solvent (D), based on the total weight of components (A), (B1), optionally (B2), (C), and (D), at an average polymerization temperature such that the decomposition half-life of said initiator (C) is between 40 and 500 minutes, in such a way that the proportion of unconverted grafting monomer (B1) and optional monomer (B2) and initiator (C) in the reaction mixture is always maintained quantitatively insufficient relative to said copolymer backbone (A); Preferably, it comprises polymerizing at least one vinyl ester monomer (B1) and optionally at least one other monomer (B2) in the presence of at least one polymer backbone (A), a free radical-forming initiator (C), and optionally up to 50% by weight of at least one organic solvent (D), based on the total weight of components (A), (B1), optional (B2) and (C), at an average polymerization temperature such that the decomposition half-life of said initiator (C) is between 40 and 500 minutes, in such a way that the proportion of unconverted grafting monomer (B1) and optional (B2) and initiator (C) in the reaction mixture is always maintained quantitatively insufficient relative to said polymer backbone (A), 2. A process for producing a graft polymer according to claim 1, wherein preferably at least 10 wt. % of the total weight of vinyl ester monomers (B1) are selected from vinyl acetate, vinyl propionate, and vinyl laurate, more preferably vinyl acetate and vinyl laurate, most preferably vinyl acetate, the remaining amount of vinyl esters can be any other known vinyl ester, preferably at least 60, more preferably at least 70, even more preferably at least 80, even more preferably at least 90 wt. % of vinyl acetate, most preferably essentially only vinyl acetate (i.e. about 100 wt. % or even 100 wt. % vinyl acetate) is used as vinyl ester (wt. % based on the total weight of vinyl ester monomers B1 used), and - if (B2) is present - the weight ratio of optional monomer (B2) to monomer (B1) is less than 0.5, preferably less than 0.4, more preferably less than 0.3, even more preferably less than 0.2, most preferably less than 0.

1.

7. 7. The process of claim 6, wherein essentially no monomers (B2) are used other than the monomer(s) (B1).

8. 7. The process of claim 6, wherein the process comprises at least one further process step selected from i) to iv): i) post-polymerization; ii) purification; iii) concentration; and iv) drying.

9. The process comprises: i) a post-polymerization process step carried out after the main polymerization reaction, in which preferably a further amount of said initiator (optionally dissolved in said solvent(s)) is added over a period of from 0.5 hours up to 3 hours, preferably about 1-2 hours, more preferably about 1 hour, and in which said radical initiator and said solvent(s) for said initiator are typically, and preferably, the same as the solvent for said main polymerization reaction; after said polymerization reaction and before said post-polymerization reaction, preferably before initiating said post-polymerization reaction by starting the addition of further radical initiator, a period of waiting is performed until said main polymerization reaction only proceeds, such period being preferably from 10 minutes up to 4 hours, preferably up to 2 hours, even more preferably up to 1 hour, most preferably up to 30 minutes; a process step in which the temperature of said post-polymerization process step is, preferably, the same as that of said main polymerization reaction or is increased, such increase being preferably by about 5-40°C, preferably by 10-20°C, compared to the temperature of said main polymerization reaction; ii) subjecting the graft polymer obtained from the main polymerization or, if carried out, from the post-polymerization process, to a concentration and / or drying procedure to remove part or almost all (as far as their boiling points allow) of volatile substances such as residual solvent(s) and / or residual monomers, a) said concentration is carried out by removing said solvent(s) and optionally also a portion of the volatile substances, preferably by applying a distillation process such as thermal distillation or vacuum distillation, preferably vacuum distillation, to increase the solid polymer concentration until a desired solid content is achieved, preferably until a desired portion or all of the volatile components, such as volatile solvents and / or unreacted volatile monomers, have been removed; b) the drying is carried out by subjecting the graft polymer, which contains at least a residual amount of volatile substances such as residual solvent and / or unreacted monomers, to a means for removing said volatile substances, such as drying using a roller drum, spray drying, vacuum drying, or freeze drying, preferably—mainly for cost reasons—spray drying; optionally combining such a drying process step with a means of agglomeration or granulation to obtain agglomerated or granulated graft polymer particles, such processes preferably being selected from spray agglomeration, granulation, or drying in a fluidized bed dryer, spray granulator, or the like; 7. The process of claim 6, comprising at least one further process step selected from:

10. 7. The process of claim 6, wherein the amount of water is low, preferably less than 5% by weight, more preferably less than 1% based on the total solvent.

11. in compositions that are fabric care and home care products, cleaning compositions, institutional and corporate cleaning products, cosmetics or personal care products, oil field formulations such as emulsion breakers for crude oil, pigment dispersions for inks such as inkjet inks, electroplating products, cementitious compositions, lacquers, paints, agrochemical formulations, Preferably, in cleaning compositions and / or fabric care and home care products: More preferably, the use of at least one grafted polymer according to claim 1 or obtained or obtainable by the process according to claim 6 in a cleaning composition for fabric care and home care, said cleaning composition being preferably a laundry detergent formulation or a dishwashing detergent formulation, Preferably, such cleaning compositions further comprise at least one enzyme selected from one or more of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, deoxyribonucleases, xylanases, oxidoreductases, dispersins, mannanases, and peroxidases, as well as combinations of at least two of the aforementioned types, preferably at least one enzyme selected from one or more of lipases, hydrolases, amylases, proteases, cellulases, more preferably at least one lipase; the at least one grafted polymer is present in an amount ranging from about 0.01% to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1% to about 10%, and most preferably from about 0.5% to about 5%, based on the total weight of such composition or product; - Use wherein such product or composition further comprises from about 1% to about 70% by weight of a surfactant system.

12. 10. A composition that is a laundry detergent, dishwashing composition, cleaning composition, and / or fabric care and home care product, comprising at least one grafted polymer according to claim 1 or obtained or obtainable by the process according to claim 6.

13. i) an antimicrobial agent selected from the group consisting of 2-phenoxyethanol; preferably, the antimicrobial agent is present in an amount ranging from 2 ppm to 5% by weight of the composition; more preferably, the antimicrobial agent comprises 0.1 to 2% phenoxyethanol. ii) 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.

13. The composition of claim 12, further comprising at least one of i) and ii):

14. 13. A method of protecting the composition of claim 12 from microbial contamination or growth, comprising adding an antimicrobial agent selected from the group consisting of 2-phenoxyethanol to the composition, the composition being an aqueous composition comprising water as a solvent.

15. 13. A method of laundering fabrics or cleaning hard surfaces, comprising treating the fabrics or hard surfaces with the composition of claim 12, wherein the composition comprises 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%, each by weight of the composition.

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