Biodegradable Graft Polymers

Abstract

The present invention relates to novel graft polymers comprising a polymer backbone (A) as graft substrate with 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), where - if present - the weight ratio of monomer (B2) to monomer (B1) is less than 0.5. The polymer backbone (A) is obtainable by polymerization of ethylene oxide and the molecular weight Mn of the polymer backbone in g / mol is within 500-5000. The present invention further relates to a process for obtaining such graft polymers, which is preferably carried out by free radical polymerization. The present invention also relates to the use of such graft polymers, for example in fabric and home care products. Fabric and home care products containing such graft polymers are also claimed.

Description

[Technical field]

[0001] The present invention relates to novel graft polymers comprising a polymer backbone (A) as graft substrate with 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 - but not preferably - further monomers (B2), where - if present - the weight ratio of monomer (B2) to monomer (B1) is less than 0.5. The polymer backbone (A) is obtainable by polymerization of ethylene oxide, the molecular weight Mn of the polymer backbone in g / mol being within 500-5000. The present invention further relates to a process for obtaining such graft polymers, which process is preferably carried out by free radical polymerization. Furthermore, the present invention relates to the use of such graft polymers, for example in fabric and home care products. Another subject of the present invention is therefore fabric and home care products containing such graft polymers. [Background technology]

[0002] Various countries have already introduced initiatives to ban microplastics, especially in cosmetics. Beyond this ban on insoluble microplastics, serious discussions are taking place regarding future regulations for soluble polymers used in consumer products. Therefore, there is a strong desire to identify new and better biodegradable raw materials for such applications. This problem is mainly acute for polymers produced by radical polymerization 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 industrially important radical-produced graft polymers of polyethylene glycol backbones show only limited biodegradability in wastewater. However, the polymers described by the present invention are preferably produced by radical graft polymerization and offer 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 polymerization of a vinyl ester component (B), the 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. WO 2007 / 138053 does not contain any disclosure regarding the biodegradability (also called "biodegradation") of the respective graft polymers disclosed therein, nor the graft polymers as defined in the present invention.

[0004] WO 03 / 042262 relates to a graft polymer comprising (A) a polymeric graft backbone without 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 vinyl ester monomers in each polymeric side chain grafted onto the backbone. Furthermore, WO 03 / 042262 does not make any disclosure related to the biodegradability of the graft polymers disclosed therein.

[0005] US-A5,318,719 relates to a new class of biodegradable water-soluble graft copolymers with builder, anti-filming, dispersing and threshold crystallization inhibition properties, comprising (a) an acid-functional monomer and, optionally, (b) another water-soluble monoethylenically unsaturated monomer copolymerizable with (a), grafted to a biodegradable substrate comprising polyalkylene oxide and / or polyalkoxylated material. However, US-A5,318,719 requires that each side chain of the graft polymer must contain a large amount of an acid-functional monomer, such as acrylic acid or methacrylic acid. Such types of 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 a vinyl ester, such as vinyl acetate. However, US 2019 / 0390142 does not disclose the graft polymer as is currently needed.

[0007] WO 2020 / 005476 discloses a fabric care composition comprising a graft copolymer and a so-called processing adjuvant, where the graft copolymer comprises a polyalkylene oxide, preferably polyethylene oxide, as the backbone, based on ethylene oxide, propylene oxide or butylene oxide, and N-vinylpyrrolidone and vinyl esters as grafted side chains on the backbone, where the backbone and both monomers are in a specific ratio.

[0008] WO 2020 / 264077 discloses a cleaning composition containing a combination of an enzyme and a polymer, which is 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, graft polymers as defined in the present invention are not disclosed.

[0009] WO 0018375 discloses a pharmaceutical composition comprising a graft polymer obtained by polymerization of at least one vinyl ester of an aliphatic C1-C24 carboxylic acid with a vinyl ester, preferably vinyl acetate, in the presence of a polyether. In the most preferred version, the graft polymer is prepared from grafting vinyl acetate onto a PEG of Mw 6000 g / mol, followed by hydrolysis of the vinyl acetate to alcohol (which would therefore be similar to the polymer obtained from the hypothetical monomer "vinyl alcohol"). The main use is the formation of coatings and films on solid pharmaceutical dosage forms such as tablets, etc.

[0010] As polymer backbones in WO 0018375, polyethers are disclosed having number average molecular weights in the range of less than 500 000, preferably in the range of 300-100 000, particularly preferably in the range of 500-20 000 and very particularly preferably in the range of 800-15 000 g / mol. It is further stated that it is advantageous to use homopolymers or copolymers of ethylene oxide having an ethylene oxide content of 40-99% by weight, and therefore preferably a content of ethylene oxide units in the ethylene oxide polymers of 40-100 mol % is used. 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 and copolymers of ethylene oxide, propylene oxide and at least one butylene oxide. The ethylene oxide content in the copolymer is preferably stated to be in the range of 40-99 mol%, the propylene oxide content in the copolymer to be in the range of 1-60 mol%, and the butylene oxide content in the copolymer to be in the range of 1-30 mol%. Linear as well as branched homopolymers or copolymers are said to be usable as graft substrates for grafting.

[0011] However, in WO 0018375 only PEG 6000 and 9000, "polyethylene glycol / polypropylene glycol block copolymer" (average molecular weight of about 8000) and "polyglycerol" (average molecular weight of 2200) are exemplified. Only five examples use vinyl acetate and only one example uses vinyl acetate and methyl methacrylate as monomers. No other monomers are exemplified. All examples use hydrolysis of the polymerized vinyl acetate monomer as a final step.

[0012] Therefore, polymers containing unhydrolyzed vinyl acetate as claimed in the present invention were not produced or characterized in WO 0018375.

[0013] Also, the specific graft polymers prepared from low molecular weight polyethylene oxide polymers as the polymer backbone as currently desired are not disclosed or claimed in WO 0018375.

[0014] The present disclosure therefore focuses on a different composition comprising only medium to high molecular weight PEG that is grafted with vinyl acetate and then hydrolyzed to vinyl alcohol for use as a film-forming polymer in pharmaceutical applications.

[0015] Also, the use of such polymers disclosed herein for detergent and cleaning or fabric care applications is not disclosed in WO 0018375. No such applications or uses are mentioned in this disclosure. Summary of the Invention [Problem to be solved by the invention]

[0016] The object of the present invention is to provide novel grafted polymers which, in addition, should have beneficial properties in terms of their biodegradability and / or cleaning behavior when used in compositions, such as cleaning compositions. [Means for solving the problem]

[0017] The object is a grafted polymer, (all percentages as weight percent based on the total weight of the grafted polymer): (A) a polymer backbone as a graft substrate, which can be obtained by polymerization of 20 to 95% ethylene oxide, and the molecular weight Mn of the polymer backbone in g / mol is within 500 to 5000; (B) 5 to 80% of polymeric side chains (B) grafted onto the polymer backbone, which are 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; This is achieved by a graft polymer comprising: DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The grafted polymers according to the present invention can be used, for example, in cleaning compositions and / or fabric care and home care products.They lead to at least comparable and preferably even improved anti-redeposition and cleaning performance in such compositions or products, for example in terms of soil redeposition and soil removal, compared to the corresponding polymers or grafted polymers according to the prior art.Furthermore, the grafted polymers according to the present invention lead to improved biodegradability when used in such compositions or products, for example, cleaning compositions and / or fabric care and home care products.

[0019] The grafted polymers with improved biodegradation according to the invention can be advantageously used in cleaning and washing compositions, where they notably aid in the removal of hydrophobic soils from textiles or hard surfaces by surfactants, thus improving the cleaning and washing performance of the formulations. Moreover, they allow the removed soils to be better dispersed in the washing or washing liquor and prevent their redeposition on the surface of the washed or cleaned material.

[0020] As used herein, the articles "a" and "an," when used in a claim, are understood to mean one or more of what is claimed or described. As used herein, the terms "comprises" and "including" are meant to be open-ended.

[0021] The compositions of the present disclosure can "comprise" (i.e., contain other ingredients), "consist essentially of" (contain primarily or almost exclusively the mentioned ingredients, with other ingredients only in very small amounts, primarily as impurities), or "consist" (i.e., contain only the mentioned ingredients, plus possibly and preferably only impurities that are unavoidable in the technical circumstances).

[0022] Similarly, the terms "substantially free of" or "substantially free of" or "essentially (free / free of)" may be used herein; this means that the indicated material is at the very minimum not intentionally added to the composition to form part of it, or preferably is not present at levels detectable by analysis. It is meant to encompass compositions in which the indicated material is present only as an impurity in one of the other intentionally included materials. The indicated material may be present, if at all, at levels of less than 1%, or even less than 0.1%, or even less than 0.01%, or even 0% by weight of the composition.

[0023] The term "about" as used herein encompasses both the exact numerical value "X", for example referred to as "about X%", and smaller variations of X, including minus 5 to plus 5%, preferably minus 2 to plus 2%, more preferably minus 1 to plus 1%, even more preferably minus 0.5 to plus 0.5% and smaller variations from X (setting X as 100% for this calculation). Of course, in cases where a given numerical value X is itself already "100%" (e.g., for purity, etc.), the term "about" clearly can and therefore only refers to deviations smaller than "100".

[0024] The phrase "fabric care composition" is meant to include compositions and formulations designed to treat fabrics. Such compositions include, but are not limited to, laundry washing compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric cleaning compositions, laundry pre-wash agents, laundry pre-treatment agents, laundry additives, spray products, dry cleaning agents or compositions, laundry rinsing additives, washing additives, post-rinse fabric treatment agents, ironing aids, unit dose formulations, delayed delivery formulations, detergents and compositions contained on or in porous substrates or nonwoven sheets, and other suitable forms that may be apparent to those skilled in the art in light of the teachings herein and the detailed description herein below. Such compositions may be used as laundry pre-treatment agents, laundry post-treatment agents, or may be added during the rinsing or washing cycle of laundry operations and as further detailed herein below when describing the use and application of the grafted polymers of the present invention and compositions comprising such grafted polymers.

[0025] Unless otherwise stated, all component or composition levels refer to the active portion of that component or composition and exclude impurities, such as residual solvents or by-products, that may be present in commercial sources of such component or composition.

[0026] All temperatures herein are in degrees Celsius (°C) unless otherwise indicated. All measurements herein are made at 20°C and at atmospheric pressure unless otherwise indicated. In all embodiments of the present disclosure, all percentages are by weight of the total composition unless otherwise indicated. All ratios are by weight unless otherwise indicated.

[0027] Graft Polymer A first subject of the invention is therefore a graft polymer, (all percentages being expressed as percentages by weight relative to the total weight of the graft polymer): (A) a polymer main chain as a graft substrate, which can be obtained by polymerization of 20 to 95%, preferably 30 to 90%, more preferably 40 to 85%, and most preferably 50 to 80% of ethylene oxide, and the molecular weight Mn of the polymer main chain in g / mol is within 500 to 5000, preferably 3500 or less, more preferably 3000 or less, even more preferably 2500 or less, and most preferably 2000 or less, for example 1800 or less; (B) 5 to 80%, preferably 10 to 70%, more preferably 15 to 60%, and most preferably 20 to 50% of polymer side chains (B) grafted onto the polymer main chain; and is obtainable by polymerization of at least one vinyl ester monomer (B1) and optionally at least one other monomer (B2), where - 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, and - most preferably - essentially no monomer (B2) is present.

[0028] The ratio of polymer backbone (A) to polymer side chain (B) in the graft polymer as exemplified in the present invention cannot be limited to a specific value; any ratio known to those skilled in the art can be used in principle. However, good results are obtained when using the ratio as detailed above.

[0029] The polymer backbone (A) itself and methods for preparing such copolymer backbones are known to those skilled in the art, typically the polymerization of ethylene oxide using known means.

[0030] Thus, suitable polymer backbones (A) for use within the present invention can be obtained by standard alkoxylation polymerization processes using ethylene oxide.

[0031] In an alternative embodiment, the present invention provides a method for producing a composition comprising: (A) a polymer backbone as a graft substrate, which can be obtained by polymerization of ethylene oxide; (B) polymeric side chains grafted onto the polymeric backbone, which can be obtained 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, and P = [molecular weight of polymer backbone in g / mole] x [percentage of amount of polymer side chain (B) based on total polymer weight, with polymer weight set to "1" and the percentage of amount of (B) as its fraction] is in the range of 50 to 1500, preferably 1200 or less, more preferably 1000 or less, even more preferably 800 or less, most preferably 600 or less, for example 400 or less or even 300 or less, and preferably at least 100, more preferably at least 120.

[0032] The graft polymers according to the present invention preferably have low polydispersity.

[0033] The graft polymers of the present invention and / or as detailed above have a polydispersity M of less than 5, preferably less than 3.5, more preferably less than 3, most preferably in the range of 1.0 to 2.5. w / M n (where M w = weight average molecular weight, and M n = number average molecular weight; polydispersity is unitless [g / mol / g / mol]. w and / or M n The respective values ​​of can be determined as described in the experimental section below.

[0034] With regard to the graft polymer of the previous embodiment and / or as detailed above, it is further preferred that no monomer (B2) is used in the polymerization to obtain the side chains (B).

[0035] The polymer backbone (A) contained in the graft polymer according to the invention and / or as detailed above can either be capped at each end group of the backbone or can be uncapped (uncapped). Consequently, within the present invention, the copolymer backbone (A) is optionally capped at one end group or at both end groups, preferably the copolymer backbone (A) is not capped at both end groups. Capping can be carried out by the addition of C1 to C 25 This is done by alkyl groups, preferably C1 to C4 groups.

[0036] As regards the polymer side chains (B) contained in the graft polymers according to the invention, it is preferred that the polymer side chains (B) are obtained by radical polymerization of at least one vinyl ester monomer (B1).

[0037] As vinyl ester monomer (B1) at least one of vinyl acetate, vinyl propionate and vinyl laurate is selected. Besides the at least one vinyl ester monomer (B1) mentioned, further vinyl ester monomers (B1) known to those skilled in the art may be used, such as vinyl valerate, vinyl pivalate, vinyl neodecanoate, vinyl decanoate and / or vinyl benzoate.

[0038] 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 have any value known to the person skilled in the art. The amount of vinyl ester monomer (B1) is usually 1% by weight or more (relative to the sum of (B1) and (B2)).

[0039] However, in a preferred embodiment, the graft polymer of the present invention and / or as detailed above comprises polymeric side chains (B) which are obtained or can be obtained by radical polymerization of at least one vinyl ester monomer (B1) and optionally at least one other monomer (B2) in the presence of a polymeric backbone (A), wherein at least 10 weight percent of the total amount of vinyl ester monomers (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, most preferably vinyl acetate, and 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 weight percent, most preferably essentially only (i.e. about 100 weight % or even 100 weight %) vinyl acetate is used as vinyl ester (weight percentage is based on the total amount of vinyl ester monomers B1 used), preferably essentially no other monomers (B2) are used.

[0040] In yet further, even more preferred embodiments, the grafted polymer of the present invention and / or as detailed above comprises (all percentages as weight percent based on the total weight of the grafted polymer): (A) a polymer main chain as a graft substrate, which can be obtained by polymerization of 20 to 95%, preferably 30 to 90%, more preferably 40 to 85%, and most preferably 50 to 80% of ethylene oxide, and the molecular weight Mn of the polymer main chain in g / mol is within 500 to 5000, preferably 3500 or less, more preferably 3000 or less, even more preferably 2500 or less, and most preferably 2000 or less, for example 1800 or less; (B) 5 to 80%, preferably 10 to 70%, more preferably 15 to 60% and most preferably 20 to 50% of polymeric side chains (B) grafted onto the polymer backbone, which are 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; wherein at least 10 weight percent of the total amount of the at least one vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, most preferably vinyl acetate, and 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 weight percent, most preferably essentially only (i.e. about 100 weight % or even 100 weight %) vinyl acetate is used as vinyl ester (weight percentage is based on the total amount of vinyl ester monomers B1 used), - More preferably - essentially no other monomers (B2) are used.

[0041] In an alternative more preferred embodiment (of the preceding embodiment), the graft polymer of the present invention and / or as detailed above comprises (A) a polymer backbone as a graft substrate, which can be obtained by polymerization of ethylene oxide; (B) polymeric side chains grafted onto the polymer backbone, which are obtained 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; and the formula P = [molecular weight of polymer backbone in g / mole] x [percentage of amount of polymer side chain (B) based on total polymer weight, with polymer weight set to "1" and the percentage of amount of (B) as its fraction] is in the range of 50 to 1500, preferably not more than 1200, more preferably not more than 1000, even more preferably not more than 800, most preferably not more than 600, for example not more than 400 or even not more than 300 and preferably at least 100, more preferably at least 120, and at least 10 weight percent of the total amount of the at least one vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, most preferably vinyl acetate, and the remaining amount of vinyl ester 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 weight percent, most preferably essentially only (i.e. about 100 weight % or even 100 weight %) vinyl acetate is used as vinyl ester (weight percentage is based on the total weight of the vinyl ester monomers B1 used), - More preferably - essentially no other monomers (B2) are used.

[0042] The grafted polymers of the present invention may contain a certain amount of non-grafted polymers made from vinyl esters ("non-grafted side chains"), such as polyvinyl acetate when only vinyl acetate is used and / or homopolymers of vinyl esters and copolymers of vinyl esters with other monomers when further monomers are used. The amount of such non-grafted vinyl ester homopolymers and copolymers can be higher or lower depending on the reaction conditions, but should preferably be 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, such as the dosage of vinyl ester and radical initiator and their relative amounts and also the amount with respect to the main chain present. This is generally known to those skilled in the art.

[0043] The grafted polymers of the present invention can be characterized by their degree of grafting (the number of grafting sites of polymeric side chains (B) on the polymeric backbone (A)). The degree of grafting can be high or low depending on the reaction conditions. Preferably, the degree of grafting is low to moderate, more preferably low. "Low" in this embodiment means that statistically there are less than 2 grafting sites per 50 alkylene oxide units.

[0044] Adjustment of the degree of grafting and this amount of non-grafted polymer can be used to optimize performance in a particular area of ​​interest, such as a certain (e.g., detergent) formulation, area of ​​application, or desired cleaning.

[0045] 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 has been obtained as such, 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) has been completed.

[0046] Due to this 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) changes from the respective ester functional group to an alcohol functional group in the polymer side chain (B). It must be pointed out that the corresponding vinyl alcohol is not suitable for use as a monomer in the polymerization process of the polymer side chain (B) due to stability aspects. To obtain an alcohol functional group (hydroxyl substituent) in the polymer side chain (B) of the graft polymer according to the invention, the alcohol functional group is typically introduced by hydrolyzing the ester functional group of the side chain.

[0047] From a theoretical point of view, each ester functional group of the polymer side chain (B) can be replaced by an alcohol functional group (hydroxy group). In such a case, the polymer side chain is completely hydrolyzed ("saponified").

[0048] 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.

[0049] However, within this embodiment of the invention, it is preferred that the hydrolysis of the polymer side chain (B) is only carried out partially, for example to an extent of up to 20%, 40% or 60% by weight (relative to the total weight of the polymer side chains).Even more preferably within this embodiment, the polymer side chain (B) is completely or partially hydrolyzed after polymerization, preferably to an extent of up to 50% relative to the amount of the at least one vinyl ester monomer (B1) used in the polymerization.

[0050] However, in the most preferred embodiment of the invention, the polymer side chains (B) are not hydrolyzed after polymerization.

[0051] In the graft polymers of the present invention and / or as detailed above, other than those as detailed above in relation to the at least one vinyl ester monomer (B1) and the optionally present further monomer (B2), no other monomers are used in the respective polymerization process to obtain the polymeric side chain (B). However, if any further polymeric monomers are present other than the monomers 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 further monomers is less than 0.5% by weight, even more preferably less than 0.01% by weight, and most preferably, there is a complete absence of any further monomers other than the monomers (B1) and optionally (B2).

[0052] In a more preferred embodiment 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 also present in an amount of less than 1% by weight 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, apart from monomer (B1), monomer (B2) is essentially absent.

[0053] Monomer (B2) can in principle be any monomer which is polymerizable with the vinyl ester monomer (B1).

[0054] It is particularly preferred within the present invention that no monomers containing acid functionality are used, in particular the monomers used to obtain the polymeric side chains (B) of the graft polymer according to the invention do not comprise any acid functional monomers such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, vinylacetic acid or acryloxypropionic acid, etc.

[0055] The polymers of the present invention have at least one, and preferably two or more of the following properties in order to be successfully used in the various application fields covered by the present invention: a) a level of biodegradability, such biodegradability of the grafted polymer being at least 30, preferably at least 35, even more preferably at least 40%, such as at least 45, 50, 55, 60, 65, 70, 75, 80 or 85%, within 28 days when tested under OECD 301F (measurement method, see experimental section). b) some degree of water solubility of the polymer so that it can be used in the aqueous environments typically present in such application fields as are generally addressed by the present invention. Preferably, the polymers of the present invention should exhibit moderate to good solubility, more preferably very good solubility, in the environments of aqueous formulations typically used in such fields for various types of formulations, such as dishwashing, automatic dishwashing, hard surface cleaning, fabric cleaning, fabric care, cosmetic formulations, etc. c) The viscosity of the polymer solution should be such that at a suitably high solids concentration of the polymer it can be handled and provided to the user during and after production, which may be as an aqueous solution containing a solvent, typically water and an organic solvent, for example as a "pure" (and therefore typically liquid) product dissolved in only water or only organic solvent, the viscosity of such polymer or polymer solution being in a range that allows typical technological process steps, such as pouring, pumping, metering, etc. Thus, the viscosity should preferably be in the range of at most about less than 4000 mPas, more preferably at most 3500 mPas, even more preferably at most 3000 mPas, such as at most 4500, 3750, 3250, 2750, etc., or up to 2600, such as 2500, 2000, 1750, 1500, 1250, 1000, 750, 500, 250, 200, 150 or 100 mPas, at a polymer concentration of 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 (based on the total solids content of the polymer in the solution as defined by the weight percent of the dry polymer within the total weight of the polymer solution). Viscosity can be measured at either 25°C or at elevated temperatures, such as 50°C or even 60°C. This allows suitable handling of the polymer solution on a commercial scale. Of course, depending on the amount of solvent added, it is clear that the viscosity will decrease if the amount of solvent increases and vice versa, thus allowing adjustment if desired. It is also clear that the measured viscosity depends on the measurement temperature, for example the viscosity of a given polymer of a given solids content of 80% by weight will be higher when measured at a lower temperature and lower when measured at a higher temperature. In a preferred embodiment, no additional solvent is added, but the as-prepared polymer solids content is between 70 and 99% by weight, more preferably between 75 and 85% by weight.In a more preferred embodiment, no additional solvent is added, but the solids content of the as-prepared polymer is between 70 and 99% by weight, more preferably between 75 and 95% by weight, and the viscosity, measured at 60° C., is less than 3000 mPas, more preferably less than 3250, even less than 2750, less than 2600, less than 2500, less than 2000, less than 1750, less than 1500, less than 1250, less than 1000, less than 750, less than 500 or even less than 250 mPas. The viscosity may be measured as is generally known for such polymers, preferably as described below in the experimental part.

[0056] In order to achieve these requirements a), b) and / or c), the following guidance can be given as to how to achieve such properties of the polymers of the present invention: Biodegradability is generally enhanced by at least one of the following conditions: · the molecular weight of the polymer backbone (A) is lower compared to the higher molecular weight; · A lower weight percentage of polymer side chains (monomer B) is grafted onto the backbone compared to a higher weight percentage.

[0057] Of course, as a further criterion, the individual performance of specific polymers must be evaluated and thus graded for each individual formulation in specific application field.Due to the wide range of usefulness of the polymers of the present invention, a comprehensive overview is not possible, but this specification and examples provide guidance on how to prepare and select useful polymers with desired properties and how to adjust properties to desired needs.One such criterion for the field of home care and especially fabric care is of course performance during washing, for example, when a specific material that shows the soiling of a specific material is subjected to a prescribed washing procedure.

[0058] The examples provide some guidance for application to the general area of ​​fabric cleaning, i.e. fabric care.

[0059] Depending on the particular need for a polymer exhibiting defined biodegradability, water solubility and viscosity (i.e., handling properties), the general and specific teachings herein will guide methods for obtaining such a polymer - without intending to be limited to the specific examples presented.

[0060] process Another subject of the present invention is a process for the preparation of the inventive graft polymer as described above, in its various embodiments and variants. Within this process for obtaining at least one graft polymer according to the invention, at least one monomer (B1) and optionally further monomers (B2) are polymerized in the presence of at least one polymer backbone (A).

[0061] It should be noted that the grafting processes by which a polymer backbone, such as polymer backbone (A), is grafted with polymer side chains are known per se to those skilled in the art. Any process known to those skilled in the art in this respect can be used within the present invention.

[0062] Within the process of the invention, the polymeric side chains (B) are preferably obtained by radical polymerization.

[0063] Radical polymerization is also known per se to those skilled in the art. Those skilled in the art are also aware that the process of the invention can be carried out in the presence of a radical-forming initiator (C) and / or at least one solvent (D). Those skilled in the art are aware of the respective components per se.

[0064] The term "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, including suitable control agents, are known to those skilled in the art.

[0065] In a preferred embodiment, the process for the preparation of the graft polymer of the present invention and / or as detailed above comprises the polymerization of at least one vinyl ester monomer (B1) and optionally at least one further 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, based on the total of components (A), (B1), optionally (B2) and (C), at an average polymerization temperature at which the initiator (C) has a decomposition half-life of 40 to 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 in quantitative deficiency relative to the copolymer backbone (A). In a preferred embodiment, monomer (B2) is not used.

[0066] The amount of ((free) radical-forming) initiator (C) is preferably 0.1 to 5% by weight, in particular 0.3 to 3.5% by weight, in each case based on the polymer side chains (B).

[0067] For the process according to the invention, it is preferred that the steady-state concentration of radicals present at the average polymerization temperature is substantially constant and that 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). This allows the reaction to be controlled and graft polymers can be prepared in a controlled manner with the desired low polydispersity.

[0068] - In order to ensure a safe temperature control, especially when the polymerization starts at high solids concentrations or with a large amount of monomer present in bulk and / or from the start, it is recommended and therefore preferred to use additional and efficient means to control the temperature. This can be done by external and / or internal cooling; such cooling can be done by internal and / or external coolers such as heat exchangers or by using reflux coolers when working at the boiling temperature of the solvent or solvent mixture at a given temperature / pressure combination.

[0069] The same procedure can of course be used with respect to the preferred embodiment mentioned above, in which the monomer is added over an extended period of time, and therefore the monomer concentration in the reaction volume is always low over time.

[0070] However, under such conditions, temperature control is usually not of critical importance since the temperature is also at least partially controlled by the propagation of the polymerization reaction by controlling the radical concentration and the availability of polymerizable monomer. Naturally, depending on the scale of the polymerization reaction, such additional cooling as described above becomes necessary for 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 - when the scale becomes large enough that the volume to surface ratio of the polymerization mixture becomes very large.

[0071] However, this is generally known to those skilled in the art of commercial scale polymerization and can therefore be adapted to the needs.

[0072] The term "average polymerization temperature" is intended herein to mean that the process is substantially isothermal, but due to the exothermic nature of the reaction there may be temperature fluctuations which are preferably kept within a range of + / - 10°C, more preferably within a range of + / - 5°C.

[0073] According to the present invention, the (radical-forming) initiator (C) at the average polymerization temperature should have a decomposition half-life of 40 to 500 minutes, preferably 50 to 400 minutes, more preferably 60 to 300 minutes.

[0074] According to the invention, the initiator (C) and the grafting monomers (B1) and / or (B2) are advantageously added in such a way that a low and substantially constant concentration of undecomposed initiator and grafting monomers (B1) and / or (B2) is present in the reaction mixture. The proportion of undecomposed initiator in the overall reaction mixture is preferably not more than 15% by weight, in particular not more than 10% by weight, based on the total amount of initiator metered in during the monomer addition.

[0075] In a more preferred embodiment, the process comprises the polymerization of 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, based on the total of components (A), (B1), optional (B2) and (C), at an average polymerization temperature at which the initiator (C) has a decomposition half-life of 40 to 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 in quantitative deficiency with respect to the polymer backbone (A), Preferably at least 10 weight percent of the total amount of vinyl ester monomers (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, most preferably vinyl acetate, the remaining amount of vinyl esters being 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 weight percent, most preferably essentially only (i.e. about 100 weight % or even 100 weight %) vinyl acetate is used as vinyl ester (weight percentages 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 and most preferably less than 0.1.

[0076] In an even more preferred embodiment of the preceding embodiment, essentially no monomer (B2) is used other than the vinyl ester monomer (B1).

[0077] The average polymerization temperature is suitably in the range of 50 to 140°C, preferably 60 to 120°C, and more preferably 65 to 110°C.

[0078] Examples of suitable initiators (C) having a decomposition half-life of 20 to 500 minutes in the temperature range of 50 to 140° C. include: - tert-C4~C 12 Alkyl hydroperoxide and tert-(C9-C 12 Aralkyl)hydroperoxide O-C2~C 12 Acylated derivatives, 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; - tert-C8~C 14 Di-O-C4-C of alkylene bisperoxide 12 Acylated derivatives, such as 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, and 1,3-di(2-neodecanoylperoxyisopropyl)benzene; - Ji (C2~C 12alkanoyl) 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)carbonate tert-C4 to C5 alkyl, for example, peroxy(2-ethylhexyl)carbonate tert-amyl; - Peroxydicarbonate (C2-C 12 alkyl), such as di(n-butyl) peroxydicarbonate and di(2-ethylhexyl) peroxydicarbonate. It is.

[0079] Depending on the average polymerization temperature, examples of particularly suitable initiators (C) are: At an average polymerization temperature of 50 to 60°C, 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; At an average polymerization temperature of 60 to 70°C, tert-Butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxypivalate and di(2,4-dichlorobenzoyl)peroxide; At an average polymerization temperature of 70 to 80°C, 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; At an average polymerization temperature of 80 to 90°C, 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; - At an average polymerization temperature of 90 to 100°C, tert-Butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl monoperoxymaleate, tert-amyl peroxy-2-ethylhexanoate, dibenzoyl peroxide and di(4-methylbenzoyl peroxide); At an average polymerization temperature of 100 to 110°C, tert-Butyl monoperoxymaleate, tert-butyl peroxyisobutyrate and tert-amyl peroxy(2-ethylhexyl)carbonate; At an average polymerization temperature of 110 to 120°C, tert-Butyl monoperoxymaleate, tert-butyl peroxy-3,5,5-trimethylhexanoate and tert-amyl peroxy(2-ethylhexyl)carbonate It is.

[0080] The preferred initiator (C) is a tert-C4-C5 alkyl hydroperoxide O-C4-C 12 The acylated derivatives tert-butyl peroxypivalate and tert-butyl peroxy-2-ethylhexanoate are particularly preferred.

[0081] Particularly advantageous polymerization conditions can be easily set by precise adjustment of 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.

[0082] The polymerization reaction of the present invention can preferably be carried out in the presence of small amounts of organic solvents (D). Of course, it is also possible to use mixtures of different solvents (D). It is preferable to use water-soluble or water-miscible solvents.

[0083] If the solvent (D) is used as a diluent, generally 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 in each case on the sum of the components (A), (B1), optionally (B2) and (C), is used.

[0084] Examples of suitable solvents (D) include: - 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, and 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 12alkyl) 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-C 16 (alkyl) ether; - 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 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, especially tetrahydrofuran Examples include:

[0085] Solvents (D) are advantageously those solvents which are also used to formulate the graft polymer of the invention for use (for example in cleaning and cleaning compositions) and which can therefore remain in the polymerization product.

[0086] Preferred examples of these solvents are polyethylene glycols having 2 to 15 ethylene glycol units, polypropylene glycols having 2 to 6 propylene glycol units and in particular the alkoxylation products of C6 to C8 alcohols (alkylene glycol monoalkyl ethers and polyalkylene glycol monoalkyl ethers).

[0087] Here, the highly branched C8 to C 16 Alkoxylation products of alcohols are particularly preferred, which allow the formulation of polymer mixtures which are free-flowing at 40-70° C. and have a very low polymer content at relatively low viscosity. Branching may be present in the alkyl chain of the alcohol and / or in the polyalkoxylate moiety (copolymerization of at least one propylene oxide, butylene oxide or isobutylene oxide unit). Particularly suitable examples of these alkoxylation products are 2-ethylhexanol or 2-propylheptanol alkoxylated with 1 to 15 moles of ethylene oxide, C alkoxylated with 1 to 15 moles of ethylene oxide and 1 to 3 moles of 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 moles of ethylene oxide and 1 to 3 moles of propylene oxide is preferred.

[0088] In an alternative embodiment, the polymerization is carried out using a mixture of at least one organic solvent and water.

[0089] In a further alternative embodiment, the polymerization is carried out using water as solvent (D).

[0090] The radical initiator (C) is preferably used in the form of a concentrated solution in one of the solvents mentioned above.The concentration naturally depends on the solubility of the radical initiator.The concentration is preferably as high as possible in order to make it possible to introduce as little organic solvent as possible into the polymerization reaction.If the initiator is soluble in water and therefore water is used as the solvent for introducing the initiator, the concentration is not critical in terms of the residual level of water.

[0091] In a preferred embodiment, the amount of water is low, preferably less than 5% by weight based on the total solvent, more preferably less than 1%.

[0092] In the process according to the invention, the polymer backbone (A), the grafting monomers (B1) and, if appropriate, (B2), the initiator (C) and, if appropriate, the solvent (D) are heated, usually in a reactor, to the selected average polymerization temperature.

[0093] According to the invention, the polymerization is carried out in such a way that an excess of polymer (polymer backbone (A) and formed graft polymer (B)) is always present in the reactor. The ratio of the amount of polymer to non-grafted monomer and initiator is generally greater than or equal to 10:1, preferably greater than or equal to 15:1, more preferably greater than or equal to 20:1.

[0094] The polymerization process according to the invention can in principle be carried out in various reactor types.

[0095] The reactor used is preferably a stirred tank into which is initially charged all or part of the polymer backbone (A), if appropriate the graft monomer (B1) or (B2), generally at most a portion of 15% by weight of the specified total amount of initiator (C) and solvent (D), heated to the polymerization temperature and the remaining amounts of (B), (C) and, if appropriate, (D) are preferably metered in separately. (B), (C) and, if appropriate, (D) are preferably metered in over a period of at least 2 hours, more preferably at least 4 hours and most preferably at least 5 hours.

[0096] In the case of a particularly preferred substantially solvent-free process variant, the entire amount of the polymer backbone (A) is initially charged as melt, the grafting monomers (B1) and, if appropriate, (B2) and also the initiator (C), which is preferably present in the form of a 10-50% by weight solution in one solvent (D), are metered in, the temperature being controlled in such a way that the selected average polymerization temperature is maintained on average during the polymerization, in particular in the range of + / - 10°C, in particular + / - 5°C.

[0097] In a further particularly preferred, low-solvent process variant, the procedure is as described above, except that the solvent (D) is metered in during the polymerization in order to limit the viscosity of the reaction mixture. It is possible to start the metered addition of the solvent only at a later time point after the polymerization has progressed or to add it in portions.

[0098] The polymerization can be effected under standard pressure or at reduced or elevated pressure. If the boiling points of the monomers (B1) or (B2) or the optional diluent (D) used are exceeded at the selected pressure, the polymerization is carried out with reflux cooling.

[0099] A post-polymerization process step can be added after the main polymerization reaction. For that 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 (however, such duration also depends on the reactor size), the radical initiator and the solvent for the initiator are typically - and preferably - the same as for the main polymerization reaction. Of course, a different radical initiator and / or a different solvent can be used equally well.

[0100] The temperature of the post-polymerization process step can be the same as that of the main polymerization reaction, which is preferred in the present invention, or it can be elevated, typically by about 5-40° C., preferably 10-20° C. higher.

[0101] A period of time may be waited between the post-polymerization and the main polymerization, where the main polymerization reaction is allowed to proceed, and then the post-polymerization reaction is initiated by starting the addition of additional radical initiator.

[0102] As for solvents with boiling points below about 110-120°C at atmospheric pressure, such solvents can be partially or essentially completely removed - as a purification step - by thermal or vacuum distillation or stripping with steam or a gas such as nitrogen, preferably vacuum distillation, such as stripping with steam produced from water, all at ambient or reduced pressure, while higher boiling solvents will usually remain in the resulting polymer product. If mercaptoethanol is used as a chain transfer regulator, steam distillation is the preferred step of purification. Therefore, higher boiling solvents such as 1-methoxy-2-propanol, 1,2-propanediol and tripropylene glycol will remain in the polymer product, and therefore their amount should be minimized as much as possible by using as high a concentration of radical initiator as possible, if such solvents are used only to introduce the initiator, unless such solvents also form part of the formulation the graft polymer will be used internally.

[0103] The grafted polymer of the present invention, i.e. the polymer solution obtained from the present process, may also be subjected to a means of concentration or drying.

[0104] The resulting grafted polymer solution may be concentrated by removing a portion of the solvent to increase the solid polymer concentration. This may be achieved by a distillation process such as thermal or vacuum distillation carried out until the desired solids content is reached. Such a process may be combined with a purification step as disclosed above, where 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 solvent and / or unreacted volatile monomers. The grafted polymer solution may also be further concentrated or dried by subjecting the grafted polymer solution, after the main polymerization step and any optional post-polymerization steps and any optional purification steps, to a means for partially or completely removing volatile materials, such as drying, for example roller-drum drying, spray drying, vacuum drying or freeze drying, preferably - mainly for cost reasons - spray drying. Such a drying process may also be combined with an agglomeration or granulation process, for example spray agglomeration or granulation or drying in a fluidized bed dryer.

[0105] use In principle, the grafted polymers of the present invention can be used in any application to replace conventional grafted polymers of the same or very similar composition (in terms of the polymer backbone and the relative amounts of grafted monomers, especially when the types and amounts of grafted monomers are similar or comparable), such applications being, for example:

[0106] Cosmetics, Personal Care: Such compositions and formulations include shampoos, lotions, gels, sprays, soaps, make-up powders, lipsticks, and hairsprays.

[0107] Technical applications: such compositions and formulations include use as dispersants in any kind of dispersion system, in any kind of adhesives, in non-aqueous and - preferably - aqueous liquid or solid formulations, typically a solid or liquid dispersed within another liquid or solid, in oil field applications, automotive applications, etc.

[0108] Lacquer, paint and stain formulations: Such compositions and formulations include non-aqueous and - preferably - aqueous lacquers and stains, paints and finishes.

[0109] Agricultural Formulations: Such compositions and formulations include those that contain agrochemically active materials in a liquid, semi-solid, mixed liquid-solid or solid environment.

[0110] Perfume Formulations: Such compositions and formulations include those in which perfumes are dissolved or dispersed in liquid or solid compositions to distribute evenly and / or retain their stability, e.g., to maintain their scent profile over time; also encompassed are compositions that exhibit release of perfume over time, such as extended or delayed release formulations.

[0111] Therefore, another subject of the present invention is the use of the graft polymers of the present invention and / or obtained or obtainable by the process of the present invention and / or as detailed above in technical applications such as in fabric care and home care products, in cosmetic and personal care formulations, as crude oil emulsion breakers, in 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, preferably as agrochemicals. Use in cleaning compositions and cleaning compositions and in fabric care and home care products, in particular for improved oily and greasy soil removal, removal of solid mud such as clay, prevention of greying of fabric surfaces and / or as scale inhibitors, wherein the cleaning compositions are preferably laundry detergent formulations and / or dishwashing detergent formulations, more preferably liquid laundry detergent formulations and / or liquid manual dishwashing detergent formulations, or in alternative preferred embodiments, use in agrochemical compositions, for example for use as dispersants, crystal growth inhibitors and / or solubilisers.

[0112] Other subjects of the present invention are therefore also cleaning compositions, fabric care and home care products, institutional cleaning products, cosmetics or personal care products, oil field formulations such as crude oil emulsion breakers or dispersants or gas hydrate inhibitors, pigment dispersions for example inkjet inks and inks containing the grafted polymer, electroplating products, cementitious compositions, lacquers, paints, agrochemical formulations, preferably in laundry detergents, cleaning compositions and / or fabric care and home care products, each comprising at least one grafted polymer as defined above or obtained or obtainable by the process of the present invention and / or as detailed herein.

[0113] Further subject of the present invention are fabric care and home care products, cleaning compositions, institutional cleaning products, cosmetics or personal care products, oil field formulations such as crude oil emulsion breakers, 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 according to the invention and / or as described above.

[0114] Laundry detergents, cleaning compositions and / or fabric care and home care products are known per se to those skilled in the art. Any compositions etc. known to those skilled in the art in connection with the respective uses can be used in connection with the present invention.

[0115] In a preferred embodiment, it is a cleaning composition and / or a fabric and home care product and / or an institutional cleaning product comprising at least one grafted polymer as defined above.In particular, it is a cleaning composition, preferably a laundry detergent formulation and / or a manual dishwashing detergent formulation, more preferably a liquid laundry detergent formulation and / or a liquid manual dishwashing detergent formulation, for improved cleaning performance and / or - (preferably "and") - improved anti-redeposition, e.g. with respect to solid redeposition and soil removal.

[0116] The grafted polymer aids in the removal of various hydrophobic and hydrophilic soils such as personal soils, food and grease soils, particulate soils such as clay or carbon black, grass soils, make-up, motor oil, etc. from textiles or hard surfaces by surfactants, thus improving the cleaning and washing performance of the formulation.

[0117] Furthermore, the grafted polymer also provides better dispersion of removed soil in the wash or cleaning liquor and prevents redeposition on the surface of the washed or cleaned material. In this specification, removed soil includes all typical soils present in the laundry process, such as body soil, food and grease soil, particulate soil such as clay or carbon black, grass soil, makeup, motor oil, etc. Such anti-redeposition effect can be observed for various fabric types such as cotton, polycotton, polyester, polyether / polyurea copolymer (Spandex™), etc. In addition, such anti-redeposition effect is also effective for fabrics with a fabric enhancer history or when the fabric washing is performed in the presence of fabric enhancers or other laundry adjuncts such as freshness beads or bleach.

[0118] In one embodiment, it is also preferred according to the invention that the cleaning composition additionally comprises (in addition to at least one graft polymer as described above) at least one enzyme, preferably selected from one or more of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, DNases, xylanases, oxidoreductases, dispersins, mannanases and peroxidases, and optionally further comprising at least one enzyme preferably selected from a combination of at least two of the above types, preferably the at least one enzyme being selected from lipases.

[0119] Another subject of the present invention is therefore cleaning compositions, such as fabric care and home care products and institutional (I&I) cleaning products, comprising at least one grafted polymer as defined above, in particular for improved cleaning and anti-redeposition performance (action as detailed above).

[0120] At least one grafted polymer as described herein is present in said cleaning compositions of the invention at a concentration 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; such cleaning compositions may further comprise - and preferably do comprise - from about 1% to about 70% by weight of a surfactant system.

[0121] Preferably, such cleaning compositions of the present invention are fabric and home care products or institutional (I&I) cleaning products, preferably fabric and home care products, more preferably laundry detergents or manual dishwashing detergents comprising at least one grafted polymer of the present invention and optionally further comprising at least one surfactant or surfactant system, providing improved soil removal, dispersion and / or emulsification and / or modification of treated surfaces and / or whiteness maintenance of treated surfaces.

[0122] Even more preferably, it comprises at least one grafted polymer of the invention and optionally further comprises at least one surfactant or surfactant system - as detailed above. The cleaning compositions of the present invention are for cleaning and anti-redeposition performance within laundry and manual dishwashing applications, and more particularly for improved cleaning and anti-redeposition performance (action as detailed above) of fabrics, tableware and the like, and may additionally comprise at least one enzyme selected from the list consisting of, and optionally further comprising, at least one enzyme, preferably selected from one or more of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, DNases, xylanases, oxidoreductases, dispersins, mannanases and peroxidases and combinations of at least two of the above types, preferably selected from one or more of lipases, hydrolases, amylases, proteases, cellulases and combinations of at least two of the above types, and more preferably the at least one enzyme is selected from lipases.

[0123] In one embodiment of the present invention, the grafted polymers of the present invention can be used for improved cleaning and anti-redeposition performance (actions as detailed above), for example for primary cleaning and / or soil removal of particulate soils and / or oily and greasy soils, and / or additionally preferably for whiteness maintenance in laundry care. In another preferred embodiment, the grafted polymers of the present invention can be used for reducing the graying of fabrics (anti-graying), preferably for more than one of the above-mentioned actions as present, i.e. improved cleaning, anti-redeposition, primary cleaning, soil removal of particulate soils and / or oily and greasy soils, whiteness maintenance and / or anti-graying, exhibited by the grafted polymers of the present invention.

[0124] In one preferred embodiment, the cleaning composition of the present invention is a liquid or solid laundry detergent composition.

[0125] 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 manual or automatic dishwashing, preferably a liquid manual dishwashing detergent composition. Such compositions are known to those skilled in the art.

[0126] In another embodiment, the cleaning compositions of the present invention are hard surface cleaning compositions that can be used to clean a variety of surfaces such as hard wood, tile, ceramic, plastic, leather, metal, glass, and the like.

[0127] In another embodiment, the cleaning compositions are designed for use in cosmetic, personal care and pet care compositions such as shampoo compositions, personal wash formulations, liquid or bar soaps.

[0128] In one embodiment, the grafted polymer of the present invention may be utilized in a cleaning composition comprising a surfactant system comprising a C10-C15 alkyl benzene sulfonate (LAS) as a first surfactant base and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants or mixtures thereof.

[0129] In a further embodiment, the graft polymer of the present invention can be utilized in cleaning compositions such as any type of laundry detergents and the like, comprising a C8 to C18 linear or branched alkyl ether sulfate having 1 to 5 ethoxy units as a first surfactant and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants or mixtures thereof.

[0130] In a further embodiment, the grafted polymer of the present invention may be utilized in cleaning compositions such as any type of laundry detergent comprising a C12-C18 alkyl ethoxylate surfactant having 5-10 ethoxy units as a first surfactant and one or more additional surfactants selected from anionic, cationic, amphoteric, zwitterionic or other non-ionic surfactants or mixtures thereof.

[0131] 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 manual dishwashing detergent formulation, each of which additionally comprises at least one surfactant, preferably at least one anionic surfactant.

[0132] In a further embodiment, the present invention also encompasses a composition comprising a graft polymer as hereinbefore described, further comprising an antimicrobial agent as hereinbefore disclosed, 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; even more preferably, comprising 0.1 to 2% phenoxyethanol.

[0133] In a further embodiment, the present invention also encompasses a method of preserving an aqueous composition against microbial contamination or growth, such composition comprising a grafted polymer as described hereinbefore, 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.

[0134] 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 manual dishwashing composition, even more preferably a liquid laundry detergent composition or a liquid softener composition for use in laundry, such composition comprising a grafted polymer as hereinbefore described, such composition 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.

[0135] In a further embodiment, the present invention also encompasses a method of laundering a fabric or cleaning a hard surface, which method comprises treating the fabric or hard surface with a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dishwashing composition, even more preferably a liquid laundry detergent composition or a liquid softener composition for use in laundry, each of which comprises a grafted polymer as hereinbefore described, and such composition further comprises 4,4'-dichloro 2-hydroxydiphenyl ether.

[0136] The selection of the additional surfactant in these embodiments can depend on the application and the desired benefit.

[0137] Description of cleaning compositions, formulations and their ingredients As used herein, the phrase "cleaning composition" includes compositions and formulations designed to clean soiled materials, including those designed to clean any type of soiled material or surface.

[0138] "Industrial cleaning" compositions include those cleaning compositions that are designed for use in industrial cleaning, such as hard surface cleaners for any type of surface, including tiles, carpets, PVC surfaces, wood surfaces, metal surfaces, lacquered surfaces, and the like, for use in cleaning any type of soiled material or surface.

[0139] "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 auxiliaries, spray products, dry cleaning agents or compositions, laundry rinsing additives, cleaning additives, post-rinse fabric treatments, ironing auxiliaries. Dishwashing compositions, hard surface cleaning compositions, unit dose formulations, delayed delivery formulations, detergents contained on or in porous substrates or nonwoven sheets, light duty liquid detergent compositions, heavy duty liquid detergent compositions, detergent gels commonly used for laundry, bleaching compositions, laundry auxiliaries, fabric enhancer 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 compositions for fabric care and home care are laundry cleaning compositions, laundry care products or laundry cleaning products, most preferably liquid laundry detergent formulations or liquid laundry detergent products.

[0140] The cleaning compositions of the present invention may be in any form, i.e., "liquid" compositions, including liquid-containing composition types such as pastes, gels, emulsions, foams, and mousses; solid compositions such as powders, granules, microcapsules, beads, noodles, pearlescent spheres, agglomerates, tablets, granular compositions, sheets, lozenges, beads, fibrous articles, bars, flakes, or mixtures thereof; delivered in single, udal, or multi-compartment sachets or containers; single-phase or multi-layer unit doses; spray or foam detergents; pre-moistened wipes (i.e., cleaning compositions combined with nonwoven materials such as those discussed in U.S. Pat. No. 6,121,165 to Mackey et al.); dry wipes that are activated with water by the user or consumer (i.e., cleaning compositions combined with nonwoven materials such as those discussed in U.S. Pat. No. 5,980,931 to Fowler et al.); and other homogeneous, heterogeneous, or single-phase or multi-phase cleaning product forms.

[0141] The composition can be enclosed in a single or multi-compartment pouch. A multi-compartment pouch can have at least two, at least three or at least four compartments. A multi-compartment pouch contains compartments that are side-by-side and / or overlapping. The composition contained in the pouch or its compartments can be a liquid, a solid (such as a powder) or a combination thereof.

[0142] Non-limiting examples of "liquids" / "liquid compositions" include light and heavy duty liquid detergent compositions, fabric enhancers, detergent gels commonly used for laundry, bleaches, and laundry aids. Gases, e.g., suspended bubbles, or solids, e.g., particles, may be contained within the liquid.

[0143] The liquid cleaning compositions of the present invention preferably have a viscosity of 50-10000 mPa·s, the liquid manual dishwashing compositions (also liquid manual "dishwashing compositions") preferably have a viscosity of 100-10000 mPa·s, more preferably 200-5000 mPa·s, and most preferably 500-3000 mPa·s, at 20 1 / s and 20°C; the liquid laundry cleaning compositions preferably have a viscosity of 50-3000 mPa·s, more preferably 100-1500 mPa·s, and most preferably 200-1000 mPa·s, at 20 1 / s and 20°C.

[0144] 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 as a 10% product concentration in demineralized water at 25°C. For example, NaOH may be used, and the actual weight % of NaOH may vary and be adjusted to a desired pH, such as pH 8.0. In one embodiment of the present invention, the pH may be adjusted to above 7 by using amines, preferably alkanolamines, more preferably triethanolamine.

[0145] Detergent compositions, such as fabric care and home care products and formulations for institutional cleaning, more specifically laundry and manual dishwashing detergents, 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 the context of the present invention by including at least one of the polymers of the present invention, preferably at least one polymer, in such compositions in an amount suitable for developing certain properties, especially when such compositions are used in their field of use.

[0146] An aspect of the present invention is also the use of the polymers of the present invention as additives for detergent formulations, in particular for liquid detergent formulations, preferably concentrated liquid detergent formulations, or as single mono-dose agents for washing.

[0147] The cleaning compositions of the present invention may - and preferably do - contain auxiliary cleaning additives (also abbreviated herein as "adjuncts"), such adjuncts preferably being in addition to the surfactant system as defined above.

[0148] Suitable auxiliary cleaning additives include builders, co-builders, surfactant systems, fatty acids and / or salts thereof, structurants, thickeners and rheology modifiers, clay / soil removal / anti-redeposition agents, polymeric foreign body release agents, dispersants such as polymeric dispersants, polymeric grease cleaners, solubilizers, amphoteric copolymers (including those without vinylpyrrolidone), chelating agents, enzymes, enzyme stabilization systems, encapsulated benefit agents such as encapsulated fragrances, bleaching compounds, bleaching agents, bleach activators, These include bleach catalysts, catalytic materials, brighteners, malodor control agents, pigments, dyes, opacifiers, pearlescent agents, color correctors, dye transfer inhibitors, fabric softeners, carriers, suds boosters, suds suppressors (defoamers), coloring particles, silver care agents, tarnish and / or corrosion inhibitors, alkalinity sources, pH adjusters, pH buffers, hydrotropes, scrubbing particles, antibacterial and antimicrobial agents, preservatives, antioxidants, softeners, carriers, fillers, solvents, processing aids, fragrance precursors, and fragrances.

[0149] Adjuvants may be present in the composition at levels suitable for the intended use of the composition, with typical use levels ranging from as low as 0.001% by weight of the composition for adjuvants such as optical brighteners to up to 50% by weight of the composition for builders.

[0150] In addition to the surfactant system and grafted polymer, the liquid cleaning composition may additionally comprise - and preferably comprises at least one of - rheology control / regulators, emollients, moisturizers, skin rejuvenation actives, and solvents.

[0151] The solid composition may additionally comprise - and preferably comprises at least one of - fillers, bleaching agents, bleach activators and catalytic materials.

[0152] Suitable examples of such cleaning adjuncts and levels of use can be found in WO 99 / 05242, U.S. Pat. Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1.

[0153] Those skilled in the art will appreciate that a detersive surfactant includes any surfactant or mixture of surfactants that provides cleaning, stain removal or laundering benefits to soiled materials.

[0154] Therefore, cleaning compositions of the present invention, such as fabric care and home care products and formulations for institutional cleaning, more particularly laundry and manual dishwashing detergents, preferably additionally comprise a surfactant system, such as those described in more detail above and below, and more preferably also comprise adjuvants.

[0155] The surfactant system may 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 understand that a surfactant system for a detergent includes any surfactant or mixture of surfactants that provides cleaning, soil removal, or laundering benefits to soiled materials.

[0156] The cleaning compositions of the present invention preferably comprise a surfactant system in an amount sufficient to provide the desired cleaning characteristics. In some embodiments, the cleaning composition comprises from about 1% to about 70% of a surfactant system by weight of the composition. In other embodiments, the liquid cleaning composition comprises from about 2% to about 60% of a surfactant system by weight of the composition. In further embodiments, the cleaning composition comprises from about 5% to about 30% of a surfactant system by weight of the composition. The surfactant system may comprise a cleaning surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof.

[0157] Laundry Compositions In laundry formulations, anionic surfactants usually make up by far the largest proportion of surfactants in such formulations. Therefore, 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.

[0158] Mula The composition according to the invention may contain at least one builder. In the context of the present invention, no distinction will be made between builders and those components elsewhere called "cobuilders". Examples of builders are complexing agents, also referred to hereinafter as complexing agents, ion exchange compounds, dispersants, scale inhibitors and precipitants. The builders are selected from citrates, phosphates, silicates, carbonates, phosphonates, aminocarboxylates and polycarboxylates.

[0159] In one embodiment of the invention, the builder is selected from polycarboxylates. The term "polycarboxylate" includes succinic acid, C2-C 16 Alkyl disuccinates, C2-C 16 Included are non-polymeric polycarboxylates such as alkenyl disuccinates, ethylenediamine N,N'-disuccinates, tartrate diacetates, alkali metal malonates, tartrate monoacetates, propane tricarboxylic acid, butane tetracarboxylic acid, and cyclopentane tetracarboxylic acid.

[0160] 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.

[0161] Suitable comonomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid. Suitable polymers have in particular weight-average molecular weights M in the range from 2000 to 40 000 g / mol, preferably from 2000 to 10 000 g / mol and in particular from 3000 to 8000 g / mol. w Further suitable copolymeric polycarboxylates are, in particular, those of acrylic acid and methacrylic acid and those of acrylic acid or methacrylic acid and maleic acid and / or its anhydrides, such as fumaric acid or maleic anhydride. Suitable copolymers are, in particular, those of acrylic acid and maleic acid with a weight-average molecular weight in the range of 2000 to 100000, preferably 3000 to 80000.

[0162] 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.

[0163] Further suitable oligomeric or polymeric polycarboxylates include graft polymers of (meth)acrylic acid or maleic acid onto polysaccharides such as degraded starch, carboxymethylated polysaccharides such as carboxymethylated cellulose, carboxymethylated inulin or carboxymethylated starch, or polyepoxysuccinic acids and their alkali metal salts, in particular their sodium salts.

[0164] Additionally, amphoteric polymers can also be used as builders.

[0165] The compositions according to the invention, especially in the case of solid formulations, may contain builders for example in a total amount ranging from 0.1 to 90% by weight, preferably from 5 to 80% by weight, preferably up to 70% by weight. Liquid formulations according to the invention preferably contain builders in the range of 0.1 to 20% by weight, such as up to 85, 75, 65, 60, 55, 50, 45, 40, 35, 30, 35, 15 or 10% by weight.

[0166] The formulation according to the invention may contain one or more alkaline carriers.

[0167] In one embodiment of the invention, the laundry formulation according to the invention additionally comprises at least one enzyme.

[0168] 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.

[0169] Such enzymes can be incorporated at a level sufficient to provide an effective amount for cleaning. A preferred amount is in the range of 0.001% to 5% by weight of active enzyme in the detergent composition according to the invention. Enzyme stabilizing systems may also be used together 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 having 1 to 3 carbon atoms per molecule and dicarboxylic acids having 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 foregoing, as well as the respective sodium and potassium salts.

[0170] Preferably, the at least one enzyme is a detergent enzyme.

[0171] In one embodiment, the enzyme is classified as an oxidoreductase (EC1), transferase (EC2), hydrolase (EC3), lyase (EC4), isomerase (EC5) or ligase (EC6). EC numbering is according to the Enzyme Nomenclature, Recommendations of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology (1992), including addenda thereto published in 1993-1999. Preferably, the enzyme is a hydrolase (EC3).

[0172] In a preferred embodiment, the enzyme is a 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, DNase, phosphodiesterase, phyta The enzyme is selected from the group consisting of: glycerylase, carbohydrase, galactanase, xanthanase, xyloglucanase, oxidoreductase, perhydrolase, aminopeptidase, asparaginase, carbohydrase, carboxypeptidase, catalase, chitinase, cyclodextrin glycosyltransferase, alpha-galactosidase, beta-galactosidase, glucoamylase, alpha-glucosidase, beta-glucosidase, invertase, ribonuclease, transglutaminase and dispersin, and combinations of at least two of the above types. More preferably, the enzyme is selected from the group consisting of protease, amylase, lipase, cellulase, mannanase, xylanase, DNase, dispersin, pectinase, oxidoreductase and cutinase, and combinations of at least two of the above types. Most preferably, the enzyme is a protease, preferably a serine protease, more preferably a subtilisin protease.

[0173] Preferably, the protease is a protease having at least 90% sequence identity with SEQ ID NO: 22 of EP1921147B1 and having the amino acid substitution R101E (according to BPN numbering). Preferably, the amylase is an amylase having at least 90% sequence identity with SEQ ID NO: 54 of WO2021032881A1.

[0174] The compositions of the invention can 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.

[0175] The enzymes may be incorporated in the composition at a level sufficient to provide an effective amount to achieve a beneficial effect, preferably with respect to a primary cleaning benefit and / or a secondary cleaning benefit, such as an anti-graying or anti-pilling benefit (e.g., in the case of cellulases). Preferably, the enzymes are present in the composition at a level of from about 0.00001% to about 5%, preferably from about 0.00001% to about 2%, more preferably from about 0.0001% to about 1% or even more preferably from about 0.001% to about 0.5% enzyme protein by weight of the composition.

[0176] Preferably, the enzyme-containing composition further comprises an enzyme stabilization system.

[0177] 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 that is compatible with the enzyme.

[0178] 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 may be added.

[0179] The compositions according to the invention may contain one or more bleaching agents.

[0180] Formulations according to the invention may contain one or more bleach catalysts.

[0181] The formulation according to the invention comprises: May contain one or more bleach activators .

[0182] The formulations according to the invention may include one or more corrosion inhibitors.

[0183] The formulation according to the invention may also comprise further cleaning polymers and / or anti-soiling polymers and / or anti-greying polymers.

[0184] Further cleaning polymers may include, without limitation, "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 in the range of 3000 to 250000, preferably 5000 to 200000, more preferably 8000 to 100000, more preferably 8000 to 50000, more preferably 10000 to 30000, and most preferably 10000 to 20000 g / mol. w Suitable polyfunctional polyethyleneimines have 80% to 99% by weight, preferably 85% to 99% by weight, more preferably 90% to 98% by weight, and most preferably 93% to 97% or 94% to 96% by weight of ethylene oxide side chains, 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 in the range of 500 to 5000 g / mol. w Preferably, a molecular weight of 500 to 1000 g / mol is used, and an M of 600 to 800 g / mol is used. w Thus, the ethoxylated polymer has an average of 5 to 50, preferably 10 to 35, and even more preferably 20 to 35 ethylene oxide (EO) units per NH functional group.

[0185] Suitable polyfunctional diamines are typically ethoxylated C2-C12 alkylenediamines, preferably hexamethylenediamine, which are further quaternized and optionally sulfated. Typical polyfunctional diamines have a weight average molecular weight M in the range of 2000-10000, more preferably 3000-8000, most preferably 4000-6000 g / mol. wIn a preferred embodiment of the present invention, an ethoxylated hexamethylenediamine, further quaternized and sulfated, may be used, which contains on average 10-50, preferably 15-40, even more preferably 20-30 ethylene oxide (EO) groups per NH group, which preferably has two cationic ammonium groups and two anionic sulfate groups.

[0186] Suitable further polyfunctional polyethyleneimines, polyfunctional diamines and oligoamines include those claimed in WO 2022 / 136408 A1, WO 2022 / 136409 A1 and WO 2021 / 165468.

[0187] In a preferred embodiment of the present invention, the cleaning composition may contain at least one multifunctional polyethyleneimine and / or at least one multifunctional diamine and / or oligoamine, in particular any of the polymers claimed therein from WO 2022 / 136408 A1, WO 2022 / 136409 A1 and / or WO 2021 / 165468, in order 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. The multifunctional polyethyleneimine or multifunctional diamine or oligoamine or mixtures thereof according to the above description may be added to the laundry detergent and cleaning composition in an amount generally as low as 0.05 to 15% by weight, preferably 0.1 to 10% by weight, more preferably 0.25 to 5% by weight, even up to 2% by weight, based on the specific overall composition, including other ingredients and water and / or solvents.

[0188] Thus, one aspect of the present invention is a laundry detergent composition, in particular a liquid laundry detergent, comprising (i) at least one inventive polymer and (ii) at least one compound selected from multifunctional polyethyleneimines and multifunctional di- and oligoamines, and mixtures thereof.

[0189] In one embodiment of the present invention, the ratio of the at least one inventive polymer to (ii) at least one compound selected from multifunctional polyethyleneimines and multifunctional 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.

[0190] Suitable anti-graying polymers include copolymers of acrylic acid or maleic acid with styrene, graft polymers of acrylic acid onto maltodextrin or carboxymethylated cellulose and the alkali metal salts thereof, especially the sodium salts thereof.

[0191] Laundry formulations containing the polymers of the present invention may also contain at least one complexing agent.

[0192] 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 invention, 1-50%, preferably 1-20% by weight of complexing agent is preferred.

[0193] Laundry formulations containing the polymers of the present invention may also contain at least one antimicrobial agent.

[0194] Antimicrobial agents are compounds that kill or inhibit the growth or reproduction of microorganisms. The microorganisms can 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.

[0195] The compositions / formulations may contain one or more antimicrobial agents and / or preservatives such as those listed on pages 35-39 of WO 2021 / 115912 A1 ("Formulations comprising a hydrophobically modified polyethyleneimine and one or more enzymes").

[0196] The following antibacterial and / or antiseptic agents: 4,4'-dichloro 2-hydroxydiphenyl ether (further names: 5-chloro-2-(4-chlorophenoxy)phenol, Diclosan, DCPP), Tinosan® HP 100 (30% by weight of DCPP in 1,2-propylene glycol); 2-phenoxyethanol (further 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 (further names: 2-bromo-2-nitro-1,3-propanediol, bronopol); glutaraldehyde (further names: 1,5-pentanedial, pentane-1,5-dial, glutaral, glutardialdehyde); glyoxal (further names: ethanedialdehyde) aldehyde, oxyaldehyde, 1,2-ethanedial; 5-bromo-5-nitro-1,3-dioxane (further names: 5-bromo-5-nitro-m-dioxane, Bronidox®); phenoxypropanol (further names: propylene glycol phenyl ether, phenoxyisopropanol, 1-phenoxy-2-propanol, 2-phenoxy-1-propanol); glucoprotamine (chemical description: reaction product of glutamic acid with alkylpropylenediamines, further name: glucoprotamine 50); cyclohexylhydroxyldiazenium-1-oxide, potassium salt (further names: N-cyclohexyl-diazenium dioxide, potassium HDO, Xyligene); formic acid (further 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 (further names: 3,5-dimethyl-1,3-5-thiadiazinan-2-thione, Dazomet;2,4-Dichlorobenzyl alcohol (further names: dichlorobenzyl alcohol, 2,4-dichloro-benzenemethanol, (2,4-dichloro-phenyl)-methanol, DCBA); 1-propanol (further names: n-propanol, propan-1-ol, n-propyl alcohol); 1,3,5-tris-(2-hydroxyethyl)-hexahydro-1,3,5-triazine (further names: hexahydrotriazine, tris(hydroethyl)-hexahydrotriazine, hexahydro-1,3-5-tris(2-hydroxyethyl)-s-triazine Azine, 2,2',2''-(hexahydro-1,3,5-triazine-1,3,5-triyl)triethanol; 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-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, such as calcium sorbate, sodium sorbate; (E,E)-hexa-2,4-dienoic acid potassium (potassium sorbate); lactic acid and its salts; L-(+)-lactic acid; in particular sodium lactate; 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, all of which are of particular interest for cleaning compositions and fabric care and home care products, especially in laundry formulations;

[0197] 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 relative to the total weight of the composition.

[0198] 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%.

[0199] 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 additional antimicrobial agent not listed here.

[0200] 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.

[0201] Further optional ingredients may be, but are not limited to, viscosity modifiers, cationic surfactants, suds boosters or suppressors, fragrances, dyes, optical brighteners, dye transfer inhibitors.

[0202] Dishwashing Composition Another aspect of the present invention is also a dishwashing composition comprising at least one inventive polymer as described above.

[0203] Thus, an aspect of the present invention is also the use of the polymers of the present invention as described above in dishwashing applications, such as manual or automatic dishwashing applications.

[0204] Dishwashing compositions according to the 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 preferred for manual dishwashing applications, while solid and sachet formulations (where the sachet may contain solids in addition to liquid components) are typically preferred for automatic dishwashing compositions, although in some parts of the world liquid automatic dishwashing compositions are used and therefore should be understood to be encompassed by the term "dishwashing composition".

[0205] Preferably, the compositions are formulated to provide superior grease cleaning (degreasing) properties, long-lasting foaming, and / or ease of viscosity control upon exposure to low temperatures; preferably at least two, more preferably all three properties are present in the dishwashing compositions of the present invention. Optional - and preferably present - additional benefits of the manual dishwashing compositions of the present invention include soil removal, shine, and / or hand protection; more preferably at least two, most preferably all three additional benefits are present in the dishwashing compositions of the present invention.

[0206] In one embodiment of the present invention, the polymer of the present invention is a component of a manual dishwashing formulation additionally comprising at least one surfactant, preferably at least one anionic surfactant.

[0207] In another embodiment of the present invention, the polymer of the present invention is a component of a manual 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 manual dishwashing formulation contains 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.

[0208] The dishwashing composition according to the invention may comprise at least one amphoteric surfactant. The addition of an amphoteric surfactant provides good foaming properties in the dishwashing composition.

[0209] Dishwashing compositions according to the present invention may comprise at least one zwitterionic surfactant.

[0210] The dishwashing composition according to the present invention may comprise at least one cationic surfactant.

[0211] The dishwashing composition according to the present invention may comprise at least one non-ionic surfactant.

[0212] Dishwashing compositions according to the present invention may include an effective amount of at least one hydrotrope to ensure compatibility of the liquid manual dishwashing detergent composition with water.

[0213] The dishwashing composition according to the present invention may comprise at least one organic solvent.

[0214] The dishwashing compositions herein may further comprise an aqueous liquid carrier, comprising 30% to 90% by weight of water, in which the other essential and optional ingredients are dissolved, dispersed or suspended. More preferably, the compositions of the present invention comprise 45% to 85% by weight, even more preferably 60% to 80% by weight of an aqueous liquid carrier. However, the aqueous liquid carrier may contain other materials that are liquid at room temperature (25° C.) or that dissolve in the liquid carrier, and that may perform some other function in addition to the function of inert filler.

[0215] The dishwashing composition according to the present invention may comprise at least one electrolyte.

[0216] Manual dishwashing formulations containing the polymers of the present invention may also contain at least one antimicrobial agent.

[0217] Examples of suitable antimicrobial agents for dishwashing compositions have already been mentioned above in relation to laundry compositions.

[0218] The antimicrobial agents may be added to the manual dishwashing compositions of the invention at a concentration of 0.0001% to 10% by weight relative to the total weight of the composition. Preferably, the formulation contains 2-phenoxyethanol at a concentration of 0.01% to 5% by weight, more preferably 0.1% to 2% by weight, and / or 4,4'-dichloro-2-hydroxydiphenyl ether at a concentration of 0.001% to 1% by weight, more preferably 0.002% to 0.6% by weight (in all cases relative to the total weight of the composition).

[0219] Further additional ingredients include, but are not limited to, conditioning polymers, cleaning polymers, surface modifying polymers, dirt 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 including NaOH and alkanolamines such as monoethanolamine, and buffering means.

[0220] Suitable examples for all of the above mentioned ingredients have already been set forth in relation to the laundry compositions above.

[0221] Common cleaning compositions and formulations Since the polymers of the invention are biodegradable, and in particular cleaning formulations typically have a pH of about 7 or more, and additionally often contain enzymes - which are included in such cleaning formulations to degrade biodegradable substances such as greases, proteins, polysaccharides, etc., present in dirt and mud and which need to be removed by the cleaning composition - some consideration must be given to formulating these biodegradable polymers of the invention. 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 polymers can be separated by adding them by coating or in separate particles that are mixed, and in the case of liquids and semi-liquids, the polymers and enzymes can be separated by formulating them in different compartments, for example in different compartments of a multi-compartment sachet or bottle with different chambers, from which the liquid is poured out simultaneously in a predetermined amount to ensure the application of the correct amount of each component at each individual use point. Such multi-compartment sachets, bottles, etc. are likewise known to the skilled person.

[0222] The liquid formulations disclosed in this section may contain, in addition to all other mentioned ingredients, 0-2%, preferably about 1%, of 2-phenoxyethanol.

[0223] The liquid formulations disclosed above and below may contain, in addition to all other mentioned ingredients, 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 mentioned ingredients, 0-0.2%, preferably about 0.15%, of 4,4'-dichloro 2-hydroxydiphenyl ether.

[0224] The formulations disclosed in this chapter may comprise - in addition to all other mentioned ingredients - one or more enzymes selected from those disclosed herein above, more preferably a protease and / or an amylase, even more preferably the protease is a protease having at least 90% sequence identity to SEQ ID NO: 22 of EP1921147B1 and having the amino acid substitution R101E (according to BPN numbering) and the amylase is an amylase having at least 90% sequence identity to SEQ ID NO: 54 of WO2021032881A1, such enzymes being preferably present in the formulation at a level of from about 0.00001% to about 5%, preferably from about 0.00001% to about 2%, more preferably from about 0.0001% to about 1% or even more preferably from about 0.001% to about 0.5% enzyme protein by weight of the composition.

[0225] The following compositions shown below, including those in the tables, disclose certain generic cleaning compositions that correspond to typical compositions associated with typical cleaning conditions as typically used in various regions and countries of the world. At least one inventive polymer may be added to such formulations in a suitable amount as outlined herein.

[0226] If a given composition does not include the grafted polymer of the present invention, such composition is a comparative composition. If it includes the grafted polymer of the present invention in the amounts described herein, inter alia, as preferred, more preferred, etc. ranges, such composition is considered to fall within the scope of the present invention.

[0227] In a preferred embodiment, the graft polymer according to the invention is used in a laundry detergent.

[0228] The liquid laundry detergent according to the present invention comprises: 0.05 to 20% of at least one inventive polymer, 1-50% surfactant, 0.1 to 40% of builders, cobuilders and / or chelating agents, 0.1~50% of other auxiliary substances, Water that adds up to 100% It consists of:

[0229] Preferred liquid laundry detergents according to the present invention include 0.5 to 15% of at least one inventive polymer, 5-40% of anionic surfactants selected from C10-C15-LAS and C10-C18 alkyl ether sulfates containing 1-5 ethoxy units, 1.5 to 10% of a non-ionic surfactant selected from C10 to C18 alkyl ethoxylates containing 3 to 10 ethoxy units; 2-20% of soluble organic builders / cobuilders selected from C10-C18 fatty acids, di- and tricarboxylic acids, hydroxydi- and hydroxytricarboxylic acids, aminopolycarboxylates and polycarboxylic acids, an enzyme system comprising 0.05 to 5% of at least one enzyme suitable for detergent use and preferably also an enzyme stabilizing system, 0.5-20% of a mono- or diol selected from ethanol, isopropanol, ethylene glycol or propylene glycol, 0.1~20% of other auxiliary substances, Water that adds up to 100% It consists of:

[0230] The solid laundry detergent according to the invention (such as a powder, granule or tablet) comprises: 0.2 to 20% of at least one inventive polymer, 1-50% surfactant, 0.1 to 90% of builders, cobuilders and / or chelating agents, 0-50% filler, 0-40% bleaching actives, 0.1-30% of other adjuvants, and / or water The sum of the components equals 100%.

[0231] Preferred solid laundry detergents according to the present invention include 0.5 to 10% of at least one inventive polymer, 5-30% of an anionic surfactant selected from C10-C15-LAS, C10-C18 alkyl sulfates and C10-C18 alkyl ether sulfates containing 1-5 ethoxy units; 1.5 to 7.5% of a nonionic surfactant selected from C10 to C18 alkyl ethoxylates containing 3 to 10 ethoxy units; 20-80% of an inorganic builder selected from sodium carbonate, sodium bicarbonate, zeolites, 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, an enzyme system containing 0.1 to 5% of at least one enzyme suitable for detergent use and preferably also an enzyme stabilizing system, 0.5-30% bleach activator, 0.1~20% of other auxiliary substances, Water that adds up to 100% It consists of:

[0232] In a preferred embodiment, the polymers according to the present invention are used in manual dishwashing detergents.

[0233] The liquid manual dishwashing detergent according to the present invention comprises: 0.05 to 10% of at least one inventive polymer, 1-50% surfactant, 0.1~50% of other auxiliary substances, Water that adds up to 100% It consists of:

[0234] A preferred liquid manual dishwashing detergent according to the present invention comprises: 0.2 to 5% of at least one polymer of the invention, 5-40% of an anionic surfactant selected from C10-C15-LAS, C10-C18 alkyl ether sulfates and C10-C18 alkyl sulfates containing 1-5 ethoxy units; 2-10% cocamidopropyl betaine, 0-10% lauramine oxide, 0-2% of a non-ionic surfactant, preferably a C10-Guerbet alcohol alkoxylate; 0-5% of an enzyme, preferably an amylase, preferably also an enzyme stabilizing system, 0.5-20% of a mono- or diol selected from ethanol, isopropanol, ethylene glycol or propylene glycol, 0.1~20% of other auxiliary substances, Water that adds up to 100% It consists of:

[0235] [Table 1]

[0236] [Table 2]

[0237] [Table 3]

[0238] Further exemplary liquid detergent formulations LD1, LD2 and LD3 are shown in the following three tables (numbers: wt. % active substance).

[0239] [Table 4]

[0240] [Table 5]

[0241] [Table 6]

[0242] All three previous tables for LD1, LD2, LD3: * "Grafted polymer" = (polyethylene glycol of Mn 6000 g / mol as graft substrate, grafted with 40 wt% vinyl acetate based on total polymer weight; produced according to the general disclosure of WO2007138054A1)

[0243] [Table 7]

[0244] In each laundry detergent, cleaning composition and / or fabric care and home care product, the at least one grafted polymer is preferably present in a concentration of from about 0.01% to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1% to about 10%, most preferably from about 0.5% to about 5%, by weight based on the total weight of such composition or product, respectively, including all numbers of concentrations therebetween and all ranges arising from the selection of any of the recited lower limits, further including 0.2, 0.3, 0.4, 1, 1,5, 2, 2.5, 3, 3.5 and 4, in combination with any of the recited upper limits and including 19, 18, 17, 16, 14, 13, 12, 11, 9, 8, 7 and 6.

[0245] Specific embodiments as described throughout this disclosure are encompassed by the present invention as part of the present invention; various additional options disclosed herein as "optional," "preferred," "more preferred," "even more preferred," or "most preferred" options of specific embodiments may be individually and independently selected (unless such independent selection is impossible by the nature of the feature or where such independent selection is expressly excluded) and thus combined within any of the other embodiments (where other such options and preferences may also be individually and independently selected), and each and any and all such possible combinations are included as individual embodiments as part of the present invention.

[0246] Most Preferred Embodiments Section The following specific embodiments further form part of the present invention.

[0247] In a first preferred embodiment, the grafted polymer of the present invention has the following properties (all percentages as weight percent based on the total weight of the grafted polymer): (B) a polymer main chain as a graft substrate, which can be obtained by polymerization of 20 to 95%, preferably 30 to 90%, more preferably 40 to 85%, and most preferably 50 to 80% of ethylene oxide, and the molecular weight Mn of the polymer main chain in g / mol is within 500 to 5000, preferably 3500 or less, more preferably 3000 or less, even more preferably 2500 or less, and most preferably 2000 or less, for example 1800 or less; (B) 5 to 80%, preferably 10 to 70%, more preferably 15 to 60% and most preferably 20 to 50% of polymeric side chains (B) grafted onto the polymer backbone, which are 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; The graft polymer comprises:

[0248] In a further most preferred embodiment, the graft polymer of the previous most preferred embodiment and particularly those of this section, (A) a polymer backbone as a graft substrate, which can be obtained by polymerization of ethylene oxide; (B) polymeric side chains grafted onto the polymer backbone, which are obtained 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; and the formula P = [molecular weight Mn of polymer backbone in g / mole] x [percentage of amount of polymer side chain (B) based on total polymer weight, with polymer weight set to "1" and the percentage of amount of (B) as its proportion] is in the range of 50 to 1500, preferably 1200 or less, more preferably 1000 or less, even more preferably 800 or less, most preferably 600 or less, for example 400 or less or even 300 or less, and preferably at least 100, more preferably at least 120.

[0249] In a further most preferred embodiment, the graft polymer of the previous most preferred embodiment and particularly those of this section, i) comprising a polymer backbone (A) which has one or two hydroxyl groups as two end groups or which may be capped at one or both ends with a C1-C22 alkyl group, preferably a C1-C4 alkyl group; and / or ii) having a polydispersity Mw / Mn (where Mw=weight average molecular weight and Mn=number average molecular weight in [g / mol / g / mol]) of less than 5, preferably less than 3.5, more preferably less than 3, most preferably in the range of 1.0 to 2.5; and / or iii) essentially does not contain monomer (B2) in the side chain (B).

[0250] In a further most preferred embodiment, the graft polymer of any of the previous most preferred embodiments and especially those of this section contains a vinyl ester monomer (B1) selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably vinyl acetate and vinyl laurate, in a total amount of at least 10 weight percent, most preferably vinyl acetate, the remaining amount of vinyl ester 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 weight percent, most preferably essentially only (i.e. about 100 weight percent or even 100 weight percent) vinyl acetate is used as vinyl ester (weight percent is based on the total weight of vinyl ester monomer B1 used).

[0251] In a further most preferred embodiment, the graft polymer of any of the previous most preferred embodiments, and particularly those of this section, is essentially free of monomer (B2).

[0252] In a further most preferred embodiment, the graft polymer of any of the previous most preferred embodiments and particularly those of this section has a biodegradability of at least 30, preferably at least 40, even more preferably at least 50% within 28 days when tested under OECD 301F.

[0253] In a further most preferred embodiment, a process for obtaining a graft polymer as detailed in any of the embodiments detailed in the present disclosure, in particular any of the previous most preferred embodiments and in particular those of this section, is encompassed, which comprises the polymerization of 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), the polymer side chains (B) being obtained by radical polymerization using a radical-forming compound to initiate the radical polymerization.

[0254] In an even more preferred embodiment of the process as detailed herein, including in particular the processes of the preceding paragraphs in this chapter, the process comprises the polymerization of 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 total of components (A), (B1), optional (B2) and (C), at an average polymerization temperature at which the initiator (C) has a decomposition half-life of 40 to 500 minutes, wherein the proportion of unconverted graft monomer (B1) and optional monomer (B2) and initiator (C) in the reaction mixture is quantitatively insufficient relative to the polymer backbone (A). the polymerization in such a way that it is always kept, preferably at least 10 weight percent of the total amount of vinyl ester monomers (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from 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 weight percent, most preferably essentially only (i.e. about 100 weight % or even 100 weight %) vinyl acetate is used as vinyl ester (weight percentages are based on the total weight of vinyl ester monomers B1 used), - if (B2) is present - the weight ratio of optional (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.

[0255] In further most preferred embodiments of the process as detailed herein, including in particular any of the most preferred embodiments for such a process detailed hereinbefore in this section, the process essentially does not use monomer (B2) other than monomer (B1).

[0256] In further most preferred embodiments of the process as detailed herein, particularly including any of the most preferred embodiments for such process detailed hereinbefore in this section, the process comprises at least one further process step selected from i) to iv): i) post-polymerization; ii) purification; iii) concentration; and) drying.

[0257] In further most preferred embodiments of the process as detailed herein, including in particular any of the most preferred embodiments of such process detailed hereinbefore in this section, the process comprises: i) a post-polymerization process step carried out after the main polymerization reaction, preferably in which a further amount of initiator (optionally dissolved in a solvent) is added over a period of more than 0.5 hours and up to 3 hours, preferably about 1-2 hours, more preferably about 1 hour, the radical initiator and the solvent for the initiator are typically - and preferably - the same as for the main polymerization reaction, and after the polymerization reaction and before the post-polymerization reaction, a period is waited to allow the main polymerization reaction to proceed before the post-polymerization reaction is started by starting the addition of further radical initiator, 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, and the temperature of the post-polymerization process is - preferably - the same as in the main polymerization reaction or is increased, such increase being preferably by about 5-40°C, preferably by 10-20°C, higher than the temperature of the main polymerization reaction; ii) subjecting the graft polymer resulting from the main polymerization or - if carried out - a post-polymerization process - to a means of concentration and / or drying in order to remove some or almost all of the volatile substances such as residual solvents (as long as they are removable due to their boiling point) and / or residual monomers, a. Concentration is preferably carried out by removing the solvent and optionally also a portion of the volatiles to increase the solid polymer concentration by applying a distillation process such as thermal or vacuum distillation, preferably vacuum distillation, which is carried out until the desired solids content is achieved, preferably until the desired portion or all of the volatile components such as volatile solvent and / or unreacted volatile monomers are removed; b. Drying is carried out by subjecting the grafted polymer, containing at least residual amounts of volatile substances such as residual solvent and / or unreacted monomers, etc., to a means for removing volatile substances such as drying using a roller drum, a spray dryer, vacuum drying or freeze drying, preferably - mainly for cost reasons - spray drying, and optionally combining such a drying process step with a means of agglomeration or granulation to obtain agglomerated or granular grafted polymer particles, such processes being preferably selected from spray agglomeration, fluidized bed dryer, granulation or drying in a spray granulator, etc. The method further comprises at least one further process step selected from:

[0258] In further most preferred embodiments of the process as detailed herein, including in particular the most preferred embodiments thereof with respect to such process detailed in this section above, the amount of water is low, preferably less than 5% by weight, more preferably less than 1% based on total solvent.

[0259] In a further most preferred embodiment, the grafted polymer obtained according to any or any of the embodiments disclosed herein, in particular according to any of the previous most preferred embodiments in this section, is used in compositions that are fabric care and home care products, cleaning compositions, institutional cleaning products, cosmetics or personal care products, oil field formulations such as crude oil emulsion breakers, pigment dispersions for inks such as inkjet inks, electroplating products, cementitious compositions, lacquers, paints, agrochemical formulations.

[0260] In a further most preferred embodiment, the graft polymer obtained according to any or any of the embodiments disclosed in this chapter herein, in particular according to any of the previous most preferred embodiments, optionally further comprises at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, cutinases, DNases, xylanases, mannanases, dispersins, oxidoreductases, lactases and peroxidases, and combinations of at least two of the above types, more preferably the at least one enzyme selected 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 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 products or compositions are used in cleaning compositions and / or fabric care and home care products, preferably cleaning compositions for fabric care and home care, preferably laundry detergent formulations or dishwashing detergent formulations, further comprising from about 1% to about 70% by weight of a surfactant system.

[0261] In further most preferred embodiments, the compositions are also included as part of the present invention which are fabric care and home care products, cleaning compositions, institutional cleaning products, cosmetics or personal care products, oil field formulations such as crude oil emulsion breakers, 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 obtained according to any or any of the embodiments disclosed herein and in particular any of the most preferred embodiments above in this chapter.

[0262] In a further most preferred embodiment, the laundry detergent, cleaning composition or fabric care and home care product comprises at least one grafted polymer obtained by any of the embodiments or embodiments disclosed herein, in particular any of the preceding most preferred embodiments in this section, or obtained by a process as detailed in any of such embodiments disclosed herein, including in particular any of the preceding most preferred embodiments in this section that disclose such a process.

[0263] In such laundry detergent, cleaning composition or fabric care and home care product as detailed in any of the embodiments of the present invention and in particular in any of the most preferred embodiments above, at least one grafted polymer - as detailed in any of such of the embodiments disclosed herein including in particular any of the most preferred embodiments above in this section disclosing 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%, each in % by weight based on the total weight of such composition or product, most preferably up to 2%, and all numbers in between and each in % by weight based on the total weight of such composition or product, including all ranges resulting from the selection of any of the lower limits and combination of any of the upper limits, optionally selected from one or more lipases, preferably one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, cutinases, DNases, xylanases, mannases, glyceryl ester ... and optionally further comprising at least one further enzyme selected from the group consisting of 2-phenoxyethanol, 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 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, and further comprising a surfactant system at about 1% to about 70% by weight of such detergent, composition or product.

[0264] In a further embodiment, the present invention also encompasses a composition comprising a graft polymer and / or polymer backbone as described hereinbefore and in any of the most preferred embodiments in this section specifically describing such polymer and / or backbone, and further comprising an antimicrobial agent as disclosed hereinbelow, preferably selected from the group consisting of 2-phenoxyethanol, more preferably comprising said antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition, and even more preferably comprising 0.1 to 2% phenoxyethanol.

[0265] In a further embodiment, the present invention also encompasses a method of protecting an aqueous composition against microbial contamination or growth, such composition comprising a graft polymer and / or a polymer backbone as described hereinbefore and in any of the most preferred embodiments in this section specifically describing such polymers and / or backbones, such composition preferably being 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.

[0266] In a further embodiment, the present invention also encompasses a composition, preferably a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dishwashing composition, even more preferably a liquid laundry detergent composition or a liquid softener composition for use in laundry, each of which comprises a grafted polymer and / or a polymer backbone as described herein above and in any of the most preferred embodiments in this section specifically describing such polymers and / or backbones, 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.

[0267] In a further embodiment, the present invention also encompasses a method of laundering fabrics or cleaning hard surfaces, which method comprises treating a fabric or hard surface with a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dishwashing composition, even more preferably a liquid laundry detergent composition or a liquid softener composition for use in laundering, each of which comprises a grafted polymer and / or polymer backbone as described hereinbefore and in any of the most preferred embodiments in this section specifically describing such polymers and / or backbones, and such composition further comprises 4,4'-dichloro 2-hydroxydiphenyl ether.

[0268] The following examples are intended to further illustrate the present invention without limiting its scope. EXAMPLES

[0269] Polymer Measurements The K value measures the relative viscosity of a dilute polymer solution and is a relative measure of the average molecular weight. As the average molecular weight of the polymer increases for a particular polymer, the K value also tends to increase. The K value is measured in a 3 wt % NaCl solution at 23° C. and a polymer concentration of 1% polymer according to the method of H. Fikentscher in "Cellulosechemie", 1932, 13, 58.

[0270] The number average molecular weight (M n ), weight average molecular weight (M w ) and polydispersity M w / M nwas determined by gel permeation chromatography in tetrahydrofuran. The mobile phase (eluent) used was tetrahydrofuran containing 0.035 mol / L diethanolamine. The concentration of the grafted polymer in tetrahydrofuran was 2.0 mg / mL. After filtration (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 the 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. Molecular weights M ranging from 106 to 1378000 g / mol. n Poly(ethylene glycol) (PEG) standards (PL) with the formula:

[0271] 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. Oxygen consumption during this time is measured as the change in pressure inside 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 using blanks.

[0272] The following (general) procedure was carried out using materials and ratios and amounts as further indicated in Tables 1 and 2.

[0273] 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 and the amount and type of monomer for grafting thereon.

[0274] Synthetic Procedures for Inventive Polymer Examples 1 to 7 Example 1: Graft polymerization of vinyl acetate (50 wt%) onto PEG (Mn 600 g / mol; 50 wt%) A polymerization vessel equipped with a stirrer and reflux condenser was initially charged with 500 g of PEG under nitrogen and heated to 90° C. Feed 1, containing 3.57 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 29.86 g of tripropylene glycol, was dosed into the stirred vessel at 90° C. in 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 6.00 hours. 10 minutes after the start of Feed 1, Feed 2 (500 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate and at 90° C. within 6.00 hours. Once the feed was complete, Feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 40.12 g of tripropylene glycol, was dosed at a constant flow rate at 90° C. within 56 minutes. Once the addition of the feed 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.

[0275] Example 2: Graft polymerization of vinyl acetate (30 wt%) onto PEG (Mn 600 g / mol; 70 wt%) A polymerization vessel equipped with a stirrer and reflux condenser was initially charged with 700 g of PEG under nitrogen and heated to 90° C. Feed 1, containing 10.20 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 47.61 g of tripropylene glycol, was dosed into the stirred vessel at 90° C. in 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 6.00 hours. 10 minutes after the start of Feed 1, Feed 2 (300 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate and at 90° C. within 6.00 hours. Once the feed was complete, Feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.39 g of tripropylene glycol, was dosed at a constant flow rate at 90° C. within 56 minutes. Once the addition of the feed 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.

[0276] Example 3: Graft polymerization of vinyl acetate (30 wt%) onto PEG (Mn 1500 g / mol; 70 wt%) A polymerization vessel equipped with a stirrer and reflux condenser was initially charged with 595 g of PEG under nitrogen and melted at 90° C. Feed 1, containing 10.41 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 42.76 g of tripropylene glycol, was dosed into the stirred vessel at 90° C. in 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 6.00 hours. 10 minutes after the start of Feed 1, Feed 2 (255 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate and at 90° C. within 6.00 hours. Once the feed was complete, Feed 3, consisting of 4.16 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 16.75 g of tripropylene glycol, was dosed at a constant flow rate at 90° C. within 56 minutes. Once the addition of the feed 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.

[0277] Example 4: Graft polymerization of vinyl acetate (25 wt%) onto PEG (Mn 1500 g / mol; 75 wt%) A polymerization vessel equipped with a stirrer and reflux condenser was initially charged with 750 g of PEG under nitrogen and melted at 90° C. Feed 1, containing 3.57 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 29.86 g of tripropylene glycol, was dosed into the stirred vessel at 90° C. in 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 6.00 hours. 10 minutes after the start of Feed 1, Feed 2 (250 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate and at 90° C. within 6.00 hours. Once the feed was complete, Feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 40.12 g of tripropylene glycol, was dosed at a constant flow rate at 90° C. within 56 minutes. Once the addition of the feed 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.

[0278] Example 5: Graft polymerization of vinyl acetate (20 wt%) onto PEG (Mn 1500 g / mol; 80 wt%) A polymerization vessel equipped with a stirrer and reflux condenser was initially charged with 800 g of PEG under nitrogen and melted at 90° C. Feed 1, containing 3.57 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 29.86 g of tripropylene glycol, was dosed into the stirred vessel at 90° C. in 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 6.00 hours. 10 minutes after the start of Feed 1, Feed 2 (200 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate and at 90° C. within 6.00 hours. Once the feed was complete, Feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 40.12 g of tripropylene glycol, was dosed at a constant flow rate at 90° C. within 56 minutes. Once the addition of the feed 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.

[0279] Example 6: Graft polymerization of vinyl acetate (15 wt%) onto PEG (Mn 1500 g / mol; 85 wt%) A polymerization vessel equipped with a stirrer and reflux condenser was initially charged with 850 g of PEG under nitrogen and melted at 90° C. Feed 1, containing 3.57 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 29.86 g of tripropylene glycol, was dosed into the stirred vessel at 90° C. in 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 6.00 hours. 10 minutes after the start of Feed 1, Feed 2 (150 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate and at 90° C. within 6.00 hours. Once the feed was complete, Feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 41.00 g of tripropylene glycol, was dosed at a constant flow rate at 90° C. within 56 minutes. Once the addition of the feed 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.

[0280] Example 7: Graft polymerization of vinyl acetate (20 wt%) and vinyl laurate (5 wt%) onto PEG (Mn 1500 g / mol; 75 wt%) A polymerization vessel equipped with a stirrer and reflux condenser was initially charged with 750 g of PEG under nitrogen and melted at 90° C. Feed 1, containing 3.57 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 29.50 g of tripropylene glycol, was dosed to the stirred vessel at 90° C. in 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 6.00 hours. 10 minutes after the start of Feed 1, Feed 2 (200 g of vinyl acetate) and Feed 3 (50 g of vinyl laurate) were started and dosed to the reactor at a constant feed rate and 90° C. within 6.00 hours. Once the feed charge was complete, Feed 4 consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 40.48 g of tripropylene glycol was charged at a constant flow rate at 90° C. within 56 minutes. Once the feed addition 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 hour.

[0281] Example 8: Graft polymerization of vinyl acetate (60 wt%) onto PEG (Mn 1500 g / mol; 40 wt%) A polymerization vessel equipped with a stirrer and reflux condenser was initially charged with 400 g of PEG under nitrogen and melted at 90° C. Feed 1, containing 10.20 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 47.61 g of tripropylene glycol, was dosed into the stirred vessel at 90° C. in 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 6.00 hours. 10 minutes after the start of Feed 1, Feed 2 (600 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate and at 90° C. within 6.00 hours. Once the feed was complete, Feed 3, consisting of 4.80 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.39 g of tripropylene glycol, was dosed at a constant flow rate at 90° C. within 56 minutes. Once the addition of the feed 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.

[0282] Example 9: Graft polymerization of vinyl acetate (10 wt%) onto PEG (Mn 1500 g / mol; 90 wt%) A polymerization vessel equipped with a stirrer and reflux condenser was initially charged with 900 g of PEG under nitrogen and melted at 90° C. Feed 1, containing 5.60 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 42.88 g of tripropylene glycol, was dosed into the stirred vessel at 90° C. in 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 6.00 hours. 10 minutes after the start of Feed 1, Feed 2 (100 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate and at 90° C. within 6.00 hours. Once the feed was complete, Feed 3, consisting of 3.54 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 27.11 g of tripropylene glycol, was dosed at a constant flow rate at 90° C. within 56 minutes. Once the addition of the feed 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.

[0283] Example 10: Graft polymerization of vinyl acetate (40 wt%) onto PEG (Mn 1500 g / mol; 60 wt%) A polymerization vessel equipped with a stirrer and reflux condenser was initially charged with 560 g of PEG under nitrogen and melted at 90° C. Feed 1, containing 5.23 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 40.05 g of tripropylene glycol, was dosed into the stirred vessel at 90° C. in 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 6.00 hours. 10 minutes after the start of Feed 1, Feed 2 (374 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate and at 90° C. within 6.00 hours. Once the feed was complete, Feed 3, consisting of 3.31 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 25.32 g of tripropylene glycol, was dosed at a constant flow rate at 90° C. within 56 minutes. Once the addition of the feed 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.

[0284] Example 11: Graft polymerization of vinyl acetate (40 wt%) onto PEG (Mn 2406 g / mol; 60 wt%) A polymerization vessel equipped with a stirrer and reflux condenser was initially charged with 480 g of PEG under nitrogen and melted at 90° C. Feed 1, containing 4.48 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 34.30 g of tripropylene glycol, was dosed into the stirred vessel at 90° C. in 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 6.00 hours. 10 minutes after the start of Feed 1, Feed 2 (320 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate and at 90° C. within 6.00 hours. 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 flow rate at 90° C. within 56 minutes. Once the addition of the feed 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.

[0285] Example 12: Graft polymerization of vinyl acetate (20 wt%) onto PEG (Mn 2406 g / mol; 80 wt%) A polymerization vessel equipped with a stirrer and reflux condenser was initially charged with 420 g of PEG under nitrogen and melted at 90° C. Feed 1, containing 2.94 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.51 g of tripropylene glycol, was dosed into the stirred vessel at 90° C. in 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 6.00 hours. 10 minutes after the start of Feed 1, Feed 2 (105 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate and at 90° C. within 6.00 hours. Once the feed was complete, Feed 3, consisting of 1.86 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 14.23 g of tripropylene glycol, was dosed at a constant flow rate at 90° C. within 56 minutes. Once the addition of the feed 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.

[0286] Example 13: Graft polymerization of vinyl acetate (40 wt%) onto PEG (Mn 30 55 g / mol; 60 wt%) A polymerization vessel equipped with a stirrer and reflux condenser was initially charged with 480 g of PEG under nitrogen and melted at 90° C. Feed 1, containing 4.48 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 34.30 g of tripropylene glycol, was dosed into the stirred vessel at 90° C. in 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 6.00 hours. 10 minutes after the start of Feed 1, Feed 2 (320 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate and at 90° C. within 6.00 hours. 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 flow rate at 90° C. within 56 minutes. Once the addition of the feed 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.

[0287] Example 14: Graft polymerization of vinyl acetate (10 wt%) onto PEG (Mn 3055 g / mol; 90 wt%) A polymerization vessel equipped with a stirrer and reflux condenser was initially charged with 540 g of PEG under nitrogen and melted at 90° C. Feed 1, containing 3.36 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 25.73 g of tripropylene glycol, was dosed into the stirred vessel at 90° C. in 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 6.00 hours. 10 minutes after the start of Feed 1, Feed 2 (60 g of vinyl acetate) was started and dosed into the reactor at a constant feed rate and at 90° C. within 6.00 hours. Once the feed was complete, Feed 3, consisting of 2.12 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 16.27 g of tripropylene glycol, was dosed at a constant flow rate at 90° C. within 56 minutes. Once the addition of the feed 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.

[0288] Synthesis procedures for comparative polymers Comparative Example 1 to Comparative Example 4 Comparative Example 1: Graft polymerization of vinyl acetate (40 wt%) onto PEG (Mn 6000 g / mol; 60 wt%) A polymerization vessel equipped with a stirrer and reflux condenser was initially charged with 660 g of PEG (Mn 6000 g / mol) under nitrogen and melted at 90° C. Feed 1, containing 4.42 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 35.09 g of 1,2-propanediol, was dosed to the stirred vessel at 90° C. in 6 hours and 10 minutes. 5.56 wt. % of Feed 1 was dosed in the first 10 minutes and the remainder was dosed at a constant feed rate over 6.00 hours. 10 minutes after the start of Feed 1, Feed 2 (440 g of vinyl acetate) was started and dosed at a constant feed rate and 90° C. over 6.00 hours. Once the dosing of feeds 1 and 2 was complete, the temperature was increased to 95° C. and feed 3, consisting of 2.81 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 23.21 g of 1,2-propanediol, was dosed within 56 minutes at a constant flow rate at 95° C. Once the feed addition was complete, the mixture was stirred for 1 hour at 95° C. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0289] Comparative Example 2: Graft polymerization of vinyl acetate (30 wt%) onto PEG (Mn 6000 g / mol; 70 wt%) A polymerization vessel equipped with a stirrer and reflux condenser was initially charged with 700 g of PEG (Mn 6000 g / mol) under nitrogen and melted at 90° C. Feed 1, containing 12.24 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 50.30 g of tripropylene glycol, was dosed to the stirred vessel at 90° C. in 6 hours and 10 minutes. 5.56 wt. % of Feed 1 was dosed in the first 10 minutes, and the remainder was dosed at a constant feed rate over 6.00 hours. 10 minutes after the start of Feed 1, Feed 2 (300 g of vinyl acetate) was started and dosed at a constant feed rate and 90° C. over 6.00 hours. Once the dosing of feeds 1 and 2 was complete, the temperature was increased to 95° C. and feed 3, consisting of 4.80 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 19.70 g of tripropylene glycol, was dosed within 56 minutes at a constant flow rate at 95° C. Once the addition of the feeds was complete, the mixture was stirred at 95° C. for 1 hour. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0290] Comparative Example 3: Graft polymerization of vinyl acetate (40 wt%) onto PEG (Mn 4000 g / mol; 60 wt%) A polymerization vessel equipped with a stirrer and reflux condenser was initially charged with 600 g of PEG (Mn 4000 g / mol) under nitrogen and melted at 90° C. Feed 1, containing 3.57 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 29.90 g of tripropylene glycol, was dosed to the stirred vessel at 90° C. in 6 hours and 10 minutes. 5.56 wt. % of Feed 1 was dosed in the first 10 minutes, and the remainder was dosed at a constant feed rate over 6.00 hours. 10 minutes after the start of Feed 1, Feed 2 (400 g of vinyl acetate) was started and dosed at a constant feed rate and 90° C. over 6.00 hours. Once the dosing of feeds 1 and 2 was complete, the temperature was increased to 95° C. and feed 3, consisting of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 41.00 g of tripropylene glycol, was dosed within 56 minutes at a constant flow rate at 95° C. Once the feed addition was complete, the mixture was stirred for 1 hour at 95° C. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0291] Comparative Example 4: Graft polymerization of vinyl acetate (60 wt%) onto PEG (Mn 6000 g / mol; 40 wt%) A polymerization vessel equipped with a stirrer and reflux condenser was initially charged with 400 g of PEG (Mn 6000 g / mol) under nitrogen and melted at 90° C. Feed 1, containing 4.8 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 23.6 g of tripropylene glycol, was dosed to the stirred vessel at 90° C. in 6 hours and 10 minutes. 5.56 wt. % of Feed 1 was dosed in the first 10 minutes, and the remainder was dosed at a constant feed rate over 6.00 hours. 10 minutes after the start of Feed 1, Feed 2 (600 g of vinyl acetate) was started and dosed at a constant feed rate and 90° C. over 6.00 hours. Once the dosing of feeds 1 and 2 was complete, the temperature was increased to 95° C. and feed 3, consisting of 3.16 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 15.70 g of tripropylene glycol, was dosed within 56 minutes at a constant flow rate at 95° C. Once the feed addition was complete, the mixture was stirred for 1 hour at 95° C. Residual amounts of monomer were removed by vacuum distillation at 95° C. and 500 mbar for 1 hour.

[0292] [Table 8]

[0293] [Table 9]

[0294] Polymer Brightness and Washing Performance in Liquid Detergents The following Water Soluble Unit 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 3).

[0295] The whiteness maintenance of the polymers of the present invention is evaluated according to the Method for Evaluating Whiteness Performance of Polymers by directly comparing the whiteness performance of Reference Composition A and Test Composition B. The ΔWI(CIE) of Composition A versus Composition B is reported in Table 4 as an indication of the polymer whiteness performance benefit. The ΔSRI of Composition A versus Reference Composition B is reported in Table 5 as an indication of the polymer cleaning performance.

[0296] [Table 10]

[0297] Evaluation method for whiteness maintenance performance of detergents Exam Preparation: The following fabrics: NA polymer: PW19, available from Empirical Manufacturing Company, Cincinnati, OH, USA Knitted Cotton 1: Test fabric, Inc 403 Cotton Interlock Circular Knit CW120, available from Empirical Manufacturing Company, Cincinnati, OH, USA Polycotton is provided for whiteness benefit testing.

[0298] The "washed and FE treated" fabric was prepared according to the following method: 400 g of fabric is washed in a WE Miniwasher (3.5 liters of water) twice with 18.6 g Ariel™ Compact powder detergent at 60° C. using a short program (45 min wash cycle followed by 3 rinse cycles; total program is 90 min), twice with no detergent at 60° C. using a short program, then three times with 8.2 g Lenor™ Concentrate (fabric enhancer) during each main wash at 40° C. using a short program. The fabric is then dried in a tumble dryer on Extra Dry until dry.

[0299] The "washed" fabric was prepared according to the following method: 400 g of fabric is washed twice with 18.6 g of Ariel Compact powder detergent at 60° C. using a short program (45 min wash cycle followed by 3 rinse cycles; total program is 90 min) and twice with no detergent at 60° C. using a short program in a WE Miniwasher (3.5 liters of water). The fabric is then dried in a tumble dryer on Extra Dry until dry.

[0300] Test Method Four fabric samples are prepared: polycotton, washed; knitted cotton, washed; NA polyester, washed and FE treated; knitted, washed and FE treated.

[0301] Each sample is run in a 96-well plate simulated wash system using magnetic bearings to simulate the agitation of a typical full-scale washer according to the following conditions: 750 ppm detergent concentration, 150 μL water per well, 25° C., water hardness of 2.5 mM (2:1 Ca+2:Mg+2 molar ratio), wash pH of 8.3, 3000 ppm Arizona test dust (PTI, supplied by Powder Technology Inc).

[0302] Each polymer listed in Table 5 is added at 15 ppm of the wash liquor. 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, eight internal replicates per 96-well plate, for a total of 16 replicates per wash condition.

[0303] When the sample is dry, L*, a*, b* and CIE WI are measured for each 96-well plate spot using a Spectrolino imaging system (Gretag Macbeth, Spectro Scan 3.273). For each treatment, the average CIE WI is measured. The delta CIE WI, as reported in the table below, is the difference between the average CIE WI of the sample and the average CIE WI of the control sample without the test polymer.

[0304] The whiteness index (WI index) as measured for several different textile materials (see table below) was calculated as follows:

[0305] For the Whiteness Index, the CIE Whiteness Index formula was used and Delta WI was calculated as follows: Delta WI for substrate=WI technical-WI free "Comparative Scaling Indicator" (e.g., enumerated) = (Total (all fabrics tested with WI technique A) x 100) / Total (all fabrics tested with no WI technique) (This comparison is set to "100" for tests without grafted polymer)

[0306] [Table 11]

[0307] [Table 12]

[0308] How to evaluate the cleaning benefits of polymers The cleaning benefits of the polymers are evaluated using a Tergotometer. Some example test stains suitable for this test are: (ex) standard grass not including Equest Standard black color without Equest Todd Clay ASTM Dust Sebum Free of CFT Highly specific sebum on polycotton without CFT Equest-free burnt butter on knitted cotton Equest-free dyed bacon on knitted cotton It is.

[0309] The stains are analyzed for L, a, b values ​​using a commercially available image analysis system.

[0310] The polymers of the invention are typically formulated into a final product along with other ingredients for testing. Wash solutions are prepared by diluting the test product with water (at the specified hardness) to the specified wash concentration.

[0311] In testing the water soluble unit dose composition, an additional 47 ppm of PVOH film is also added to the tergotometer pot. The wash temperature is 30° C. and the water hardness is 8 gpg.

[0312] The fabric washed in each tergotometer pot includes two pieces of each test soil (two internal replicates), 13 swatches of 5x5cm WfK SBL 2004 soiling sheets and additional knitted cotton ballast making up to a total fabric weight of 60g.

[0313] Once all the fabrics are added into the tergotometer pot containing the wash liquor, the wash liquor is agitated for 40 minutes.The wash liquor is then poured off and the fabrics are subjected to one or two 5-minute rinse steps, after which they are drained and spun dry.The washed soils are dried in an air flow cabinet and then analyzed for L, a, b values ​​using a commercially available image analysis system.

[0314] This procedure is further repeated to give a total of 3-4 external replicates.

[0315] The Stain Removal Index (SRI) is calculated from the L, a, b values ​​using the formula shown below. The higher the SRI, the better the stain removal. SRI = 100*((ΔE b -ΔE a ) / ΔE b ) ΔE b =√((L c -L b ) 2 +(a c -a b ) 2 +(b c -b b ) 2 ) ΔE a =√((L c-L a ) 2 +(a c -a a ) 2 +(b c -b a ) 2 ) The subscript "b" indicates data for the stain before washing. The subscript "a" denotes data for stains after washing. The subscript "c" denotes data for unsoiled fabric.

[0316] The ΔSRI of composition A versus the reference composition B is reported in Table 6 as an indication of the polymer cleaning performance.

[0317] As shown in Table 6, the polymers of the present invention provide significant cleaning benefits in liquid laundry detergents, especially with respect to sebum soils.

[0318] [Table 13]

Claims

1. A graft polymer, all percentages being expressed as weight percent based on the total weight of the graft polymer: (A) a polymer backbone as a graft substrate obtainable by polymerization of 20 to 95%, preferably 30 to 90%, more preferably 40 to 85%, and most preferably 50 to 80% of ethylene oxide, the molecular weight Mn of said polymer backbone in g / mol being within the range of 500 to 5000, preferably not more than 3500, more preferably not more than 3000, even more preferably not more than 2500, and most preferably not more than 2000, for example not more than 1800; (B) 5 to 80%, preferably 10 to 70%, more preferably 15 to 60%, most preferably 20 to 50% of polymeric side chains (B) grafted onto said polymer backbone, which are 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, even more preferably less than 0.1, and most preferably (B2) is excluded. A graft polymer comprising:

2. (A) a polymer backbone (A) as a graft substrate, which can be obtained by polymerization of ethylene oxide; (B) polymeric side chains grafted onto said polymeric backbone, which are obtained 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; and the formula P = [molecular weight Mn of the polymer backbone in g / mole] x [percentage of amount of polymer side chain (B) based on total polymer weight, with polymer weight set to "1" and the percentage of amount of (B) as its fraction] The product of is in the range of 50 to 1500, preferably 1200 or less, more preferably 1000 or less, even more preferably 800 or less, most preferably 600 or less, for example 400 or less or even 300 or less, and preferably at least 100, more preferably at least 120. The graft polymer according to claim 1,

3. i), ii), iii), iv) and v): i) the polymer backbone (A) may have one or two hydroxy groups as two end groups, or may be capped at one or both ends with a C1-C22 alkyl group, preferably a C1-C4 alkyl group; ii) the graft polymer has a polydispersity Mw / Mn (where Mw = weight average molecular weight and Mn = number average molecular weight [g / mol / g / mol]) of less than 5, preferably less than 3.5, more preferably less than 3, and most preferably in the range of 1.0 to 2.5; iii) essentially no monomer (B2) is used in the polymerization to obtain the side chain (B); iv) at least 10 weight percent of the total amount of vinyl ester monomers (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from 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 weight percent, most preferably essentially only (i.e., about 100 weight percent or even 100 weight percent) vinyl acetate is used as vinyl ester (weight percent is based on the total weight of vinyl ester monomers B1 used); and v) the biodegradability of said graft polymer is at least 30, preferably at least 35, and even more preferably at least 40% within 28 days when tested under OECD 301F; The graft polymer according to claim 1, wherein at least one of the following is satisfied.

4. 2. A process for obtaining a graft polymer according to claim 1, wherein at least one vinyl ester monomer (B1) and optionally at least one other monomer (B2) are polymerized in the presence of at least one polymer backbone (A), and the polymer side chains (B) are obtained by radical polymerization using a radical-forming compound to initiate the radical polymerization.

5. The method comprises the polymerization of 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 of components (A), (B1), optional (B2) and (C), at an average polymerization temperature at which the initiator (C) has a decomposition half-life of 40 to 500 minutes, in such a way that the proportion of unconverted graft monomer (B1) and optional (B2) and initiator (C) in the reaction mixture is always kept quantitatively insufficient relative to the polymer backbone (A), preferably at least one vinyl ester monomer (B1) and optionally at least one other monomer (B2).

5. The process according to claim 4, wherein at least 10 percent by weight of the total amount of monomers (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, most preferably vinyl acetate, and 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 percent by weight, most preferably essentially only (i.e. about 100% by weight or even 100% by weight) vinyl acetate is used as vinyl ester (weight percentages are 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.

6. 5. The process according to claim 4, wherein essentially no monomer (B2) is used in addition to the monomer (B1).

7. i) to iv): i) post-polymerization; ii) purification; iii) concentration; and iv) drying.

5. The process of claim 4, comprising at least one further process step selected from:

8. i) a post-polymerization process step carried out after the main polymerization reaction, in which preferably a further amount of initiator (optionally dissolved in said solvent) is added over a period of from 0.5 hours to a maximum of 3 hours, preferably about 1-2 hours, more preferably about 1 hour, said radical initiator and said solvent for said initiator are typically—and preferably—the same as for the main polymerization reaction, and after the polymerization reaction and before the post-polymerization reaction, preferably a period is waited to allow the main polymerization reaction to proceed before the post-polymerization reaction is started by starting the addition of further radical initiator, said period preferably being from 10 minutes to a maximum of 4 hours, preferably at most 2 hours, even more preferably at most 1 hour, most preferably at most 30 minutes, and the temperature of said post-polymerization process step—preferably—is the same as in the main polymerization reaction or is increased, said increase preferably being by about 5-40°C, preferably 10-20°C, higher than the temperature of the 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 in order to remove part or almost all of the volatile substances, such as residual solvents (as long as they are removable due to their boiling point) and / or residual monomers, a. said concentration is preferably carried out by removing said solvent and optionally also a portion of the volatile materials to increase the solid polymer concentration by applying a distillation process such as thermal or vacuum distillation, preferably vacuum distillation, carried out until a desired solids content is achieved, preferably until a desired portion or all of the volatile components, such as volatile solvent and / or unreacted volatile monomers, are removed; b) 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, etc., to a means for removing said volatile substances, such as drying using a roller drum, a spray dryer, vacuum drying or freeze drying, preferably - mainly for cost reasons - spray drying, and optionally combining the drying process step with a means of agglomeration or granulation to obtain agglomerated or granular graft polymer particles, said process preferably being selected from spray agglomeration, granulation or drying in a fluidized bed dryer, spray granulation device, etc.

5. The process of claim 4, comprising at least one further process step selected from:

9. 5. The process of claim 4, wherein the amount of water is low, preferably less than 5% by weight, more preferably less than 1% by weight, based on the total solvent.

10. 10. Use of at least one grafted polymer according to claim 1 or at least one grafted polymer obtained or obtainable by the process according to claim 4 in a composition which is a fabric care and home care product, a cleaning composition, an institutional cleaning product, a cosmetic or personal care product, an oil field formulation such as a crude oil emulsion breaker, a pigment dispersion for inks such as inkjet inks, an electroplating product, a cementitious composition, a lacquer, a paint, an agrochemical formulation, preferably in a cleaning composition and / or in a fabric care and home care product, more preferably in a cleaning composition for fabric care and home care, said cleaning composition preferably being a laundry detergent formulation or a dishwashing detergent formulation, optionally comprising one or more lipases, hydrolases, amylases, proteases, hydroxybenzoates ... and at least one enzyme preferably selected from lipases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, DNases, xylanases, oxidoreductases, dispersins, mannanases, and peroxidases, and combinations of at least two of the above types, preferably the at least one enzyme is selected from lipases, hydrolases, amylases, proteases, and cellulases, and the at least one grafted polymer is present in an amount ranging from about 0.01% to about 20%, preferably 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 the composition or product, and the product or composition further comprises from about 1% to about 70% by weight of a surfactant system.

11. 10. A composition which is a fabric care and home care product, a cleaning composition, an institutional cleaning product, a cosmetic or personal care product, an oil field formulation such as a crude oil emulsion breaker, a pigment dispersion for inks such as inkjet inks, an electroplating product, a cementitious composition, a lacquer, a paint, an agrochemical formulation, preferably a laundry detergent, a dishwashing composition, a cleaning composition and / or a fabric care and home care product, comprising at least one graft polymer according to claim 1 or at least one graft polymer obtained or obtainable by the process according to claim 4, respectively.

12. 12. The composition of claim 11 further comprising an antimicrobial agent selected from the group consisting of 2-phenoxyethanol, preferably in an amount ranging from 2 ppm to 5% by weight of the composition, more preferably 0.1 to 2% phenoxyethanol.

13. 12. The composition of claim 11, comprising 4,4'-dichloro 2-hydroxydiphenyl ether at a concentration of 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6%, each by weight of the composition.

14. 12. A method of preserving a composition according to claim 11 against microbial contamination or growth, said method comprising adding to said composition an antimicrobial agent selected from the group consisting of 2-phenoxyethanol, said composition being preferably an aqueous composition comprising water as a solvent, such that said composition comprises phenoxyethanol in an amount comprising in the range of 2 ppm to 5% by weight of said composition, more preferably 0.1 to 2%.

15. 12. A method of laundering fabrics or cleaning hard surfaces, comprising treating the fabric or hard surface with the composition of claim 11, wherein the composition comprises 4,4'-dichloro 2-hydroxydiphenyl ether, preferably 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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