Biodegradable graft polymers

Abstract

The present invention relates to novel graft polymers comprising a polymer main chain (A) as a graft matrix having grafted polymer side chains (B) thereon. The polymer side chains (B) are obtainable by polymerization of at least one vinyl ester monomer (B1), optionally at least one nitrogen-containing monomer (B2), optionally a further monomer (B3). The polymer backbone (A) comprises a polyalkylene oxide-derived moiety and a moiety derived from a lactone and / or a hydroxy acid, which moieties are mixed such that the polymer backbone contains ester functional groups within the polymer chain. The invention further relates to a method for obtaining such a graft polymer, preferably by free-radical polymerization. The invention also relates to the use of such graft polymers, for example in fabrics and home care products. Also claimed are compositions and products containing such graft polymers, such as fabrics and home care products.

Description

[0001] The present invention relates to novel graft polymers which comprise a polymer backbone (A) as graft matrix, on which polymer side chains (B) are grafted. These polymer side chains (B) are obtainable by (co)polymerization of at least one vinyl ester monomer (B1), optionally a nitrogen-containing monomer (B2) and optionally further monomers (B3) and optionally further monomers. The polymer backbone (A) is made up of at least two subunits (a1) and (a2), where (a1) is derived from at least one alkylene oxide monomer and (a2) is a unit derived from at least one lactone and / or at least one hydroxy acid.

[0002] The present invention further relates to a process for obtaining such graft polymers, which process is preferably carried out by polycondensation. Furthermore, the present invention relates to the use of such graft polymers in, for example, textile and household care products. Another subject of the present invention is a composition comprising at least one graft polymer, such as textile and household care products. Background Art

[0003] Many countries have introduced initiatives to ban microplastics, especially in cosmetic products. In addition to banning insoluble microplastics, there is also a lively debate about future requirements for soluble polymers used in consumer products. Therefore, it is highly desirable to identify new and better biodegradable components for such applications. This problem is very serious for polymers produced by free radical polymerization based on a carbon-only backbone (a backbone without heteroatoms such as oxygen), because a carbon-only backbone is particularly difficult for microorganisms to degrade. Even graft polymers produced by free radical means with a polyethylene glycol backbone of industrial importance show only limited biodegradation in wastewater. However, the polymers described by the present invention are preferably prepared by free radical graft polymerization and offer enhanced biodegradation characteristics compared to the prior art.

[0004] Polyalkylene oxides are important polymers with a wide range of applications. They have been widely used as a basis for producing graft polymers which are widely used in consumer formulations, including cleaning compositions for household and other uses.

[0005] Similarly, graft polymers of vinyl esters grafted onto polyalkylene oxide-polymers such as vinyl acetate-grafted-polyethylene glycol are known polymers. Their use in the detergent field and in many other application fields is also known.

[0006] However, those polymers lack biodegradability or at least suffer from very limited biodegradability.

[0007] However, a certain amount - if not all - of such consumer products are ultimately rinsed away after their use and may ultimately end up in rivers or oceans if not biodegradable or otherwise removed in sewage treatment plants.

[0008] Therefore, biodegradability is not only one of the very important upcoming features in the detergent field, as biodegradable polymers can avoid the problem of accumulation in the environment.

[0009] According to the applicable laws of certain countries (which are expected to become law in the near future if not already implemented and effective), such problems will no longer be acceptable.

[0010] On the other hand, the functions imparted by such polymers are also of utmost importance, as they allow for high cleaning efficiency and thus, among other advantages, allow for low use of cleaning additives for a single cleaning run and thus allow for savings in the materials used and thus also avoid environmental pollution. Since those special polymers also allow for cleaning at lower temperatures, in shorter times and with lower amounts of water, they are required for environmentally friendly cleaning methods.

[0011] Therefore, providing biodegradable polymers for the detergent field is of utmost importance for solving environmental pollution problems without compromising cleaning efficiency, as such lower cleaning efficiency would not only inevitably pollute the environment.

[0012] One such widely known polymer is a graft polymer of vinyl acetate on PEG6000, where a wt. ratio of 60% (VAc) to 40% (PEG) is well-known and widely adopted for its cleaning and whiteness benefits in liquid laundry formulations (liquid and gel-like detergents).

[0013] The poor biodegradability of polyalkylene oxides decreases in the range of several hundred g / mol molecular weight up to several thousand g / mol molecular weight. Even more so, graft polymers based on such polyalkylene oxides are usually even worse in terms of their biodegradability due to the grafting.

[0014] Prior art graft polymers

[0015] US2019 / 0390142 relates to a fabric care composition comprising a graft copolymer, which can consist of: (a) a polyalkylene oxide, such as polyethylene oxide (PEG); (b) N-vinylpyrrolidone (VP); and (c) a vinyl ester, such as vinyl acetate. However, US2019 / 0390142 does not disclose the graft polymer required by the present invention.

[0016] WO 2020 / 005476 discloses fabric care compositions comprising graft copolymers and so-called processing aids, said graft copolymers comprising a polyalkylene oxide based on ethylene oxide, propylene oxide or butylene oxide, preferably polyethylene oxide, as the main chain, and N-vinylpyrrolidone and vinyl esters as graft side chains on said main chain, and wherein the main chain and the two monomers are in specific ratios.

[0017] WO 2020 / 264077 discloses cleaning compositions containing a combination of an enzyme and a polymer, such compositions being suitable for removing stains from soiled materials.

[0018] This disclosure 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.

[0019] US 31816566 discloses graft polymers of so-called "lactone polyesters" and blends thereof with PVC. The lactone polyester is a homopolymer of ε-caprolactone or a copolyester thereof with ε-alkyl-ε-caprolactone. Polymers made from lactones and alkylene oxides used as graft matrices in the present invention are not disclosed. The lactone polyesters of US 31816566 are grafted with ethylenically unsaturated monomers, and "vinyl esters of aliphatic acids" are also mentioned in a long list, in which vinyl formate, vinyl acetate and vinyl propionate are exemplified. Twenty-two examples show the use of acrylic acid, butyl acrylate, dimethylaminoethyl methacrylate, styrene, acrylonitrile and methyl methacrylate as the only monomers actually employed, all only as single monomers and without using monomer mixtures for graft polymerization. Only one example (Example 12) uses vinyl acetate as the monomer and poly-ε-caprolactone as the graft matrix (i.e., a graft matrix not containing any alkylene oxide), with 200 grams of the main chain and 30 grams of vinyl acetate, i.e., the amount of vinyl acetate based on the graft matrix of 15 wt.% is equal to 13 wt.% of vinyl acetate based on the total polymer weight. US 31816566 does not disclose anything about the biodegradation of such polymers; the only use disclosure is as a plasticizer in PVC polymers. The type of graft polymer shown in the present invention is not disclosed nor indicated.

[0020] WO 2022 / 136409 of BASF discloses amphiphilic alkoxylated polyalkyleneimines or amines; it does not disclose graft polymers comprising a polymer made from lactones and alkylene oxides as the graft backbone and grafted with ethylenically unsaturated monomers comprising at least vinyl esters in free radical polymerization. Thus, its disclosure is completely irrelevant to the present invention, except for the fact that it also aims at polymer structures for use in fields similar to those of the present invention and that those products contain lactones and alkylene oxides. The lactones and alkylene oxides are polymerized to produce a lactone-alkylene oxide-copolymer, which is attached to the amine groups of the starting compound polyethyleneimine or polyamine. After the formation of those side chains, no graft polymerization is carried out. Thus, these structures, their preparation, as well as these properties and thus the functions in the applications of such compounds are completely different. The graft polymers of the type shown in the present invention are neither disclosed nor indicated.

[0021] US2022 / 0056380 discloses cleaning compositions focused on specific enzymes and thus not focused on specific polymers themselves, their structures, preparations or properties. Among many components of such compositions, graft polymers are also mentioned as components. However, the graft polymers are typically known graft polymers (such as the preferably mentioned " HP22" of BASF) - all of which do not contain lactones in the polymer backbone, so such a backbone is made only of alkylene oxides. Those alkylene oxides - and especially the preferred polymers with a backbone molecular weight of about 6000 g / mol are not very biodegradable at all, and the graft polymers are prepared using such polyalkylene oxide-backbones with even worse biodegradability as shown in the present invention. The graft polymers of the type shown in the present invention are neither disclosed nor indicated.

[0022] All prior art graft polymers do not use polymers made from lactones and alkylene oxides as the backbone; thus, the biodegradation of those polyalkylene oxides is low or negligible, while polyesters may show good biodegradation but poor performance in the intended application fields and are also typically less suitable for graft polymerization.

[0023] At the time of filing the present invention, the task of improving the biodegradation of graft polymers based on a backbone having polyalkylene oxide-units in the backbone has been solved in the unpublished patent application PCT / EP 2022 / 065983 (now published as WO2022 / 263354), which discloses graft polymers based on a backbone comprising ester-functional groups and polyalkylene oxide-units as functional units. The backbone is prepared by oxidizing the polyalkylene oxide in a first reaction and then esterifying the oxidized PEG-mixture with itself or with an additionally added polyalkylene oxide. The backbone is then grafted with vinyl acetate.

[0024] The polymers in this disclosure undergo a two-step synthesis of the main chain: The oxidation as the first reaction step is expensive and time-consuming, and the composition obtained from the oxidation is difficult to control because - depending on the time taken for the reaction - the content of the mixture changes. Typically, the obtained mixture contains unoxidized starting materials, polyalkylene oxides with one hydroxyl group oxidized to a carboxyl functional group, and polyalkylene oxides with both ends oxidized. Therefore, the flexibility in designing the main chain is highly restricted.

[0025] This patent application also does not disclose the use of nitrogen-containing monomers for the preparation of graft polymers.

[0026] Prior art regarding the main chain

[0027] This invention discloses the use of three main types of polymer main chains comprising (oligo- / poly-)alkylene oxide moieties and (oligo- / poly-)lactone / hydroxy acid-derived moieties.

[0028] Such main chains are designated as (A1), (A2), and (A3) (see the following definitions) and are in principle known to date:

[0029] (A1)

[0030] WO 2002046268 (Cognis Corporation, now BASF SE) discloses biodegradable polymers as surfactants, emulsifiers, etc., which are obtained by reacting an organic initiator with 1. an alkylene oxide, 2. a mixture of an alkylene oxide and a lactone. "Organic initiator" is defined on page 4 as a mono-functional or multi-functional alcohol or amine.

[0031] To obtain a copolymer from an alkylene oxide and a caprolactone, a suitable starting material is reacted with a pre-mixed combination of the alkylene oxide and the caprolactone.

[0032] To obtain an (A1)-type main chain copolymer from an alkylene oxide and a lactone such as caprolactone, a suitable starting material is reacted with a pre-mixed combination of the alkylene oxide and the caprolactone.

[0033] An alcohol with 2 hydroxyl groups (diol) is used as the starting material. Examples of such diols are: ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, ethylene oxide and propylene oxide block copolymers, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc.

[0034] The alkylene oxides used in combination with caprolactone are: ethylene oxide, 1,2-propylene oxide or 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentylene oxide, preferably ethylene oxide and propylene oxide.

[0035] The copolymerization of alkylene oxides and caprolactones is carried out under typical conditions for alkoxylation reactions. Alkaline catalysts such as potassium hydroxide, sodium hydroxide, sodium methoxide, and potassium methoxide are used.

[0036] (A2)-Main-chain polymers can in principle be obtained by alkoxylation of polyesters.

[0037] Polyesters are obtainable, for example, by polymerizing lactones such as caprolactone onto starters having two hydroxyl groups (such as diols like ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, ethylene oxide and propylene oxide block copolymers, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc.).

[0038] The polymerization of caprolactone is carried out with various catalysts such as the transesterification catalyst tin(II) alkanoate.

[0039] The alkoxylation of such polycaprolactones is carried out under typical alkoxylation conditions. Due to the basic reaction conditions for alkoxylation, transesterification reactions can occur at the ester bonds of the polycaprolactone.

[0040] US 4281172 describes acrylates from polyester-polyether copolymers. To obtain these structures, polyesters of monoalcohols, diols, triols, or tetraols are reacted with alkylene oxides.

[0041] Polyester esters are synthesized according to US 3169945 from hydroxyl-containing components with various catalysts (including Ti or Sn catalysts or alkali metal hydroxides).

[0042] The alkoxylation reaction is catalyzed by BF3-etherate or potassium hydroxide, etc.

[0043] JP 07149883 describes a method for obtaining polyester-polyols by reacting a compound having at least two active hydrogens with a lactone and then with an alkylene oxide. Both reactions are carried out with the same catalyst. The catalyst is an alkali metal hydroxide or an alkali metal alcoholate.

[0044] WO 9636656 claims biodegradable alkylene oxide-lactone copolymers. These polymers are synthesized from bifunctional or polyfunctional starters, which are reacted with alkylene oxides and lactones in a copolymerization reaction and then block-capped with alkylene oxides. The catalyst is an alkali metal hydroxide or an alkaline earth metal hydroxide or a Lewis acid. The patent application describes the improved biodegradability of the claimed polymers over polyalkylene oxides and their use as surfactants, emulsifiers, etc. but not as the main chain for graft polymers.

[0045] (A3)-Main-chain polymers can in principle be obtained by the polycondensation of polyalkylene glycols with lactones, resulting in - simplified - triblock polymers.

[0046] A triblock copolymer having a middle polyalkylene oxide block and derived from caprolactone and an alkylene oxide is synthesized as follows: 1. forming a polyalkoxylate from a diol or water by reaction with an alkylene oxide, and 2. polymerizing caprolactone onto the polyalkoxylate.

[0047] Both reactions can be carried out under typical reaction conditions for the alkoxylation reaction (polyalkoxylate) and for the polymerization of caprolactone (polycaprolactone block).

[0048] Such triblock copolymers having a middle polyethylene oxide block have been known since about the 1990s. These polymers have been used for drug release and dissolution purposes (Z. Zhu et al., Journal of Polymer Science, Part A: Polymer Chemistry 1997, 35(4), 709 - 714; M. Boffito et al., Journal of Biomedical Materials Research, Part A 2015, 103A(3), 1276 - 1290).

[0049] (A4)-type backbones are also known:

[0050] WO 96 / 36656 discloses biodegradable oxide - lactone copolymers and copolyesters as already described above for (A3).

[0051] WO 2002046268 (Cognis Corporation, now BASF Corporation) discloses alkylene oxide - lactone copolymers as already described for (A1).

[0052] However, the use of such polymers as backbones for graft polymers, through which improved biodegradation is introduced into such graft polymers, is unknown.

[0053] Object of the invention

[0054] It has been recognized that graft polymers based on conventional polyalkylene oxides (without ester groups in the backbone) exhibit unexpectedly low biodegradation, which is typically much lower than the expected biodegradation percentage calculated based on the biodegradation of pure polyalkylene oxides.

[0055] Compared with unmodified polyalkylene oxides and unmodified polyalkylene glycols, graft polymers based on such conventional polyalkylene oxides generally show a decrease in biodegradation because of the increased degree of modification of the polyalkylene oxide (which is usually a polyalkylene glycol having two hydroxy end groups and is thus often referred to as a “polyalkylene glycol”) grafted to such a backbone by free radicals with polymerizable monomers (i.e., an increase in the number of side chains on the backbone). This is sometimes attributed to the blocking of the biodegradation mechanism because it appears that polyalkylene oxides / polyalkylene glycols degrade starting from their respective end groups and then along the polymer chain. Thus, any additional branching on the carbon atoms of the backbone - which occurs when polymer side chains are grafted to such a backbone - hinders and may completely stop degradation. Thus, it is proposed that the higher the degree of grafting (i.e., the more side chains attached to the backbone), the lower the percentage of biodegradation of such graft polymers. Unfortunately, it is also generally observed that with a higher degree of branching, there is an improvement in performance in the desired application because only when the amount of side chains is higher will the change in the chemical structure of the backbone be sufficient for the new graft polymer to exhibit its specific properties compared to the uniqueness of the unmodified backbone in a simple mixture of the (unattached / ungrafted) homopolymer that constitutes the side chains of the graft polymer.

[0056] Therefore, when polyalkylene oxides are used as the backbone, the difficulty of combining the conflicting properties of a suitable graft polymer with excellent application performance with the percentage of biodegradation of the unmodified backbone (i.e., unmodified polyalkylene oxide / polyalkylene glycol) has not been solved so far.

[0057] Although the unpublished patent application PCT / EP 2022 / 065983 (now published as WO 2022 / 263354) has provided a first solution to the problem of lack of biodegradation of the polyalkylene oxide backbone, the practical aspects of the solution found are still unsatisfactory because the two-step reaction is lengthy and expensive as two completely different types of chemical reactions (oxidation and polymerization) are employed and the structural changes are not easily controlled as oxidation results in a mixture of compounds as diols (i.e., starting material polyalkylene glycol), monoalcohol-mono carbonic acid (i.e., partially oxidized polyalkylene glycol), and dicarboxy-polyalkylene oxide (i.e., fully oxidized polyalkylene glycol). Structures as used herein are not obtainable by the methods disclosed in that document. Similarly, nitrogen-containing monomers are not disclosed.

[0058] Therefore, it is necessary to improve the biodegradability of the graft matrix while maintaining the general structure of the graft polymer and thus maintaining or even improving the application properties, and to improve the cost and efficiency of the unpublished patent application PCT / EP 2022 / 065983 (now published as WO 2022 / 263354) by reducing the production method to only one reaction type and simultaneously improving the variability of the chemical structure in only one reaction step.

[0059] Although polymers of types (A1), (A2) and (A3) as defined herein are known, their use for preparing graft polymers as the main chain is not yet known.

[0060] Therefore, an object of the present invention is to provide novel graft polymers based on a graft main chain of a polyalkylene oxide type imparting ester functional groups.

[0061] Furthermore, when used in compositions such as cleaning compositions, these novel graft polymers should have beneficial properties in terms of biodegradability and / or their washing behavior.

[0062] Graft polymers

[0063] The graft polymers of the present invention comprise The polymer main chain as a graft matrix as the first structural unit and Poly mer side chains as the second structural unit .

[0064] First structural unit (main chain)

[0065] First structural unit of the graft polymer is the polymer main chain serving as the graft matrix for the graft polymers of the present invention, wherein the polymer main chain (A) is obtainable by the polymerization of at least one subunit (a1) and at least one subunit (a2).

[0066] Subunit (a1) is made of at least one alkylene oxide monomer and / or at least one polyalkylene oxide-polymer having two hydroxy end groups Subunit (a2) is made of at least one lactone and / or at least one hydroxy acid, the alkylene oxide monomer is selected from C2- to C10-alkylene oxides, preferably C2 to C5-alkylene oxides, such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,2-pentylene oxide or 2,3-pentylene oxide; selected from 1,4-diols or their cyclic or oligomeric analogs, or polymeric ethers based on such 1,4-diols; selected from 1,6-diols or their cyclic or oligomeric analogs, or polymeric ethers based on such 1,6-diols; or any one of them in a mixture in any ratio, as a block of certain polymer units, or as a statistical polymer structure, or a polymer comprising one or more homopolymer blocks of a certain monomer and one or more statistical blocks comprising more than one such monomer and any combination thereof, such as a polymer having several different blocks of two or more different monomers, or blocks of two or more different monomers, blocks of a statistical mixture of two or more monomers, etc.

[0067] As used herein, the term "block (co)polymer" means that the corresponding polymer contains at least two (i.e., two, three, four, five or more) homopolymer or copolymer subunits ("blocks") connected by covalent bonds. A "diblock" copolymer has two different blocks (homopolymer and / or copolymer subunits), and a "triblock" copolymer thus has three different blocks (homopolymer and / or copolymer subunits), and so on. The number of individual blocks in such block copolymers is not limited; thus, an "n-block copolymer" contains n different blocks (homopolymer and / or copolymer subunits). In a single block, the size / length of such blocks may vary independently of other blocks. The minimum length / size of a block is based on two individual monomers (as a minimum), but can be up to 50 or even 100 or 200, and any number between 2 and 200. The corresponding monomers of the individual blocks used to prepare the block copolymer backbone (a1) can be added in sequence. However, it is also possible that there is a transition from one monomer to another resulting in a so-called "dirty structure", where at the edge / boundary of the corresponding block, a few monomers of the corresponding adjacent block may be included in the individual block under consideration (the so-called "dirty structure" or "dirty block"). However, preferably, the block copolymer subunits (a1) according to the present invention do not contain any dirty structure at the corresponding block boundaries, although for commercial reasons (i.e., mainly the cost of effectively using the reactor, etc.), a small amount of dirty structure may still be included (although not intentionally).

[0068] Preferably, at least one monomer in the polymer is derived from the use of ethylene oxide.

[0069] In another embodiment, the structure of the polymer-subunit (A1) contains more than one alkylene oxide monomer; in such a case, the polymer backbone is a random copolymer, a block copolymer or a copolymer of a mixed structure comprising block units (where each block is a homopolymeric block or a random block itself) and a statistical / random part composed of two or more alkylene oxides, wherein one of the monomers is ethylene oxide. Preferably, in addition to ethylene oxide, the other monomer is propylene oxide (PO) and / or 1,2-epoxybutane (BO), preferably only 1,2-propylene oxide.

[0070] Similarities of (A1), (A2) and (A3)

[0071] The at least one lactone and / or hydroxy acid is selected from group i) and / or ii), wherein

[0072] i) lactones, i.e. cyclic esters, starting with α-lactones (three ring atoms), followed by β-lactones (four ring atoms), γ-lactones (five ring atoms), etc.; such lactones are preferably β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, ε-caprolactone, δ-decalactone, γ-decalactone, ε-decalactone; preferably caprolactone;

[0073] and

[0074] ii) hydroxy acids, which can be derived by hydrolysis from any lactone, especially from any lactone within the previous group i), especially α-, β- or γ-hydroxy acids derived by hydrolysis from the corresponding lactone, as well as lactic acid, glycolic acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 12-hydroxystearic acid, citric acid;

[0075] Preferably lactic acid or caprolactone, more preferably caprolactone.

[0076] Depending on how the starting materials are employed and depending on the relative amounts, the subunits (a1) and (a2) can be combined in any order.

[0077] Thus, the polymer backbone (A) obtained from the reaction of (a1) and (a2) can be defined within a very wide range by selecting the desired subunits (a1) and (a2), and - within subunit (a1) by selecting the number of different alkylene oxides, their relative amounts, their order of reaction, etc., and of course also for (a2) by selecting the compounds, their relative amounts, etc., in such a way

[0078] -1) obtaining a first defined (a1)-subunit and then reacting it with the (a2)-subunit,

[0079] -2) directly reacting the monomeric alkylene oxide from subunit (a1) with the monomeric subunit (a2); or

[0080] -3) Combine the previous methods 1) and 2).

[0081] Thus, three main backbone structures can be defined and obtained:

[0082] (A1):

[0083] The subunit (a2) can be added during the polymerization of the alkylene oxide (a1-unit) to produce a random copolymer; in its variant, a polyalkylene oxide having two hydroxyl groups can be added to such a polymerization, thereby introducing a specific (a1)-subunit-block; if the alkylene oxide used is at least partially different from the alkylene oxide used to prepare the polyalkylene oxide also used, or if the structure of the polyalkylene oxide (i.e., the order of the alkyleneoxy-units therein) is different from the structure obtained by reacting the at least one alkylene oxide used for copolymerization with the (a2)-subunit and the polyalkylene oxide, then this variant is available.

[0084] In a simplified method, the (A1)-backbone can be described as a random arrangement order of (a1)-subunits and (a2)-subunits. Depending on the relative amounts of (a1) and (a2) and their reactivity, the block lengths of (a1) and (a2) vary.

[0085] Structures such as the following can be obtained by this method:

[0086] Poly[random-{lactone}-{alkylene oxide}]

[0087] ("Oligo / poly-lactone" depicts the (a2)-subunit and is thus prepared from lactone / hydroxy acid; "PAG" = polyalkylene glycol is used herein to depict the (a1)-subunit)

[0088] Therefore, in a preferred embodiment, the polymer backbone is selected from

[0089] (A1) A backbone composed of randomly arranged monomers, oligomeric and / or polymeric (a1)-subunits and monomers, oligomeric and / or polymeric (a2)-subunits, wherein there are more than one subunit (a1) and / or more than one subunit (a2).

[0090] (A2):

[0091] The subunit (a2) can be first oligomerized / polymerized and copolymerized with at least one alkylene oxide to produce a mixed random / block structure; depending on the degree of oligomerization of the lactone / hydroxy acid, and if monomeric lactone / hydroxy acid is also present when adding the alkylene oxide, the structure can be further changed by adjusting the amount and length of the (a2)-subunit-chains within the (A2)-backbone.

[0092] As (A1), in its further variants, it is also possible to add a polyalkylene oxide having two hydroxyl groups to such polymerization, thereby also introducing a specific (a1)-subunit-block; this variant is usable if the alkylene oxide used is at least partly different from the alkylene oxide used for preparing the polyalkylene oxide also used, or if the structure of the polyalkylene oxide (i.e., the sequence of the alkyleneoxy-units therein) is different from the structure obtained by reacting the at least one alkylene oxide used for copolymerization with the (a2)-subunit and the polyalkylene oxide.

[0093] In a simplified method, the (A2)-main chain can be described as a triblock polymer having an internal (a2)-block and two external (a1)-blocks.

[0094] (Switching the order to the opposite direction gives structure (A3); see below.)

[0095] Structures of the form shown below (in its simplest form) can be obtained by this method:

[0096] [PAG]-[oligo / polylactone]-[PAG]

[0097] (Here, "lactone" is used to denote the (a2)-subunit and is thus made of lactone / hydroxy acid and can be a single monomer unit or an oligomeric or polymeric unit made of the monomers in the first reaction step; "PAG" = polyalkylene glycol is used here to depict the (a1)-subunit)

[0098] In the case where the (a2)-subunit-starting material has not completely reacted when adding the alkylene oxide, the structure will no longer be a true triblock structure but will additionally contain further shorter (a2)-units in the chain and will thus consist of a multiblock structure or even turn into a mixture of block and random structure arrangements.

[0099] Thus, in a preferred embodiment, the polymer main chain is selected from the main chain of (A2) consisting of an oligomeric or polymeric subunit (a2) as the internal block and two external blocks of oligomeric and / or polymeric (a1)-subunits, which is defined as "-[(block of (a1))]-[(block of (a2))]-[(block of (a1))]-", and may also contain higher-order block polymers such as 5-block, 7-block, and 9-block, etc., where the additional blocks of (a1) and (a2) are connected at the outside of the triblock structure, such as the pentablock "[(block of (a1))]-[(block of (a2))]-[(block of (a1))]-[(block of (a2))]-[(block of (a1))]-[(block of (a2))]-[(block of (a1))]" etc.

[0100] (A3):

[0101] The sub-unit (a2) can be added after the epoxide alkane is oligomerized or (almost completely) polymerized, resulting in a block structure containing larger (a2)-chains and larger (a1)-chains; in the case where (a1) is completely polymerized before adding (a2), the resulting structure can be described as “(a2)-polyepoxide alkane-(a2)”; such structures can also be obtained by directly reacting the polyepoxide alkane with (a2). By first only oligomerizing the epoxide alkane and then reacting a mixture containing the epoxide alkane oligomer and monomeric epoxide alkane with (a2), or by reacting (a2) with the epoxide alkane and with the polyepoxide alkane polymerization, more complex structures can be obtained.

[0102] In a simplified method, the (A3)-main chain can be described as a triblock polymer having an internal (a1)-block and two external (a2)-blocks:

[0103] (Switching the order to the opposite direction gives structure (A2); see above.)

[0104] [Oligomer / polylactone]-[PAG]-[oligomer / polylactone]

[0105] (“Oligomer / polylactone” depicts the (a2)-sub-unit and is thus prepared from lactone / hydroxy acid; “PAG” = polyalkylene glycol is used here to depict the (a1)-sub-unit)

[0106] Thus, in a preferred embodiment, the polymer main chain is selected from a main chain composed of an internal block of oligomerized and / or polymerized (a1)-sub-units and two external blocks of oligomerized or polymerized sub-units (a2), which is at least in the form of a triblock polymer defined as “-[block of (a2)]-[block of (a1)]-[block of (a2)]-”.

[0107] Similar to the case of (A2), in the case where the (a2)-sub-unit starting material has not completely reacted, the structure will no longer be a true triblock structure but will additionally contain additional shorter (a1)-units in the chain and will thus consist of a multiblock structure or even turn into a mixture of block and random structure arrangements.

[0108] Second structural unit (grafted side chain)

[0109] When adding the corresponding other sub-unit substances, there are more unreacted (a2) substances (in the case of the (A2)-main chain) or more unreacted (a1) substances (in the case of the (A3)-main chain), and the difference between (A2) and (A3) is reduced.

[0110] In the extreme case, the result will be a true copolymerization of the sub-units (a1) and (a2) and will thus also be similar or even identical to (A1).

[0111] Thus, (A1), (A2), and (A3) are “merely” the extremes of the general principle of copolymerizing alkylene oxides, polyalkylene glycols, and lactones / hydroxy acids in every conceivable order, ratio, and variation of reaction time, before adding other starting materials.

[0112] Thus, in a preferred embodiment, the polymer backbone is selected from backbones obtained by the general principle of copolymerizing alkylene oxides, polyalkylene glycols, and lactones / hydroxy acids in every conceivable order, ratio, and variation of reaction time, before adding other starting materials.

[0113] (A4):

[0114] (A4) is a structure starting from an oligomeric or polymeric subunit (a1) that is capped on one side, preferably etherified with an alcohol, more preferably a short-chain alcohol C1 to C4. Then, the oligomer / polymer capped on this side of subunit (a1) is reacted with at least one subunit (a2) and optionally at least one subunit (a1) - where the subunit (a1) can be different from that / those in the starting block or can be arranged in a different order compared to those in the starting block - to attach a new block containing a portion from the subunits employed in the (co)polymerization to the uncapped side of the starting block, thereby obtaining the following diblock structure

[0115] [Capping group]-[Subunit (a1)]-[Subunit (a2)], or

[0116] [Capping group]-[Subunit (a1)]-[Random-{Subunit (a2)-Subunit (a1)}].

[0117] It should be emphasized that the oligomerization or polymerization of subunits (a1) and (a2) can each be achieved by using “initiator molecules” that are then incorporated into the oligomers and polymers of subunits (a1) and (a2). Suitable initiator molecules for such polycondensation reactions of lactones and hydroxy acids as well as alkylene oxides are known; such compounds contain at least two hydroxyl groups available for the condensation reaction, such as diols like ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, ethylene oxide and propylene oxide block copolymers, 1,2- and 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc. Water is also a suitable initiator molecule for the condensation of alkylene oxides.

[0118] Thus, the backbones (A1) to (A4) can contain portions derived from such initiator molecules, especially any one or more of the following: water, ethylene glycol, polyethylene glycol, 1,2- and 1,3-propanediol, polypropylene glycol, ethylene oxide and propylene oxide block copolymers, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol.

[0119] In cases where a compound derived from an alkylene oxide is used as the starting molecule, such uses have been described in the above main chain definitions, and thus such a starting molecule derived from an alkylene oxide can be added as a molecule or - in the case of an oligomer or polymer of an alkylene oxide - can be prepared in a first reaction step before adding the subunit (a2) for the condensation reaction. However, the use of starting molecules not derived from alkylene oxides is also covered as an option in any embodiment of any of the main chains disclosed herein; preferably, such starting molecules are used for preparing any such main chains (A1), (A2), and (A3).

[0120] A typical reaction procedure for obtaining such structures is, first, to form an oligo / polyalkoxylate from the starting molecule by reaction with an alkylene oxide (i.e., subunit (a1)), and then, second, to further condense the subunit (a2) onto the polyalkoxylate. Both reactions can be carried out under typical reaction conditions for the alkoxylation reaction (to obtain the oligo / polyalkoxylate) and for the polymerization of the subunit (a2).

[0121] The polymerization of the subunit (a2) is carried out in a known manner with various catalysts such as the transesterification catalyst tin(II) alkanoate.

[0122] The alkoxylation of such oligo / poly[(subunit (a2))] is carried out under typical, known alkoxylation conditions. Due to the basic reaction conditions for alkoxylation, transesterification reactions can occur at the ester bonds of the oligo- / poly-[(subunit (a2))], and thus compounds with a mixed random / block structure are produced.

[0123] In a preferred embodiment, the polymer main chain as the graft matrix contains at least one subunit (a1) and at least one subunit (a2), where

[0124] (a1) is a unit containing a moiety - preferably consisting essentially of - derived from at least one alkylene oxide monomer and / or at least one polyalkylene oxide-polymer having two hydroxy end groups, the alkylene oxide monomer being selected from the group of C2- to C10-alkylene oxides, preferably C2 to C5-alkylene oxides,

[0125] (a2) is a unit containing at least one lactone and / or at least one hydroxy acid (preferably consisting of), such a subunit (a2) being a moiety derived from a single lactone and / or hydroxy acid or an oligomeric or polymeric unit consisting of at least one type of lactone and / or at least one type of hydroxy acid,

[0126] where preferably the at least one lactone and / or hydroxy acid is selected from group i) and / or ii), where

[0127] i) Lactones, i.e., cyclic esters, starting with α-lactone (three ring atoms), followed by β-lactone (four ring atoms), γ-lactone (five ring atoms), etc.; such lactones are preferably β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, ε-caprolactone, δ-decalactone, γ-decalactone, ε-decalactone; preferably caprolactone;

[0128] and

[0129] ii) Hydroxy acids, which can be derived by hydrolysis from any lactone, especially from any lactone within group i) above, especially α-, β- or γ-hydroxy acids derived by hydrolysis from the corresponding lactone, and lactic acid, glycolic acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 12-hydroxystearic acid, citric acid;

[0130] preferably lactic acid or caprolactone, more preferably caprolactone,

[0131] wherein the polymer backbone is obtained by:

[0132] (A1) Copolymerization of at least one subunit (a1) and at least one subunit (a2), where optionally at least one oligomer or polymer made from at least one subunit (a1) or at least one subunit (a2) can also be used in the copolymerization of the at least one subunit (a1) and the at least one subunit (a2);

[0133] (A2) First oligomerize / polymerize the subunit (a2), and then polymerize the product with the subunit (a1);

[0134] (A3) First oligomerize / polymerize the subunit (a1), and then copolymerize the product with the subunit (a2); or

[0135] (A4) First provide an oligomeric or polymeric subunit (a1) capped on one side, preferably etherified with an alcohol, more preferably a short-chain alcohol C1 to C4, which - as a starting block - thereafter reacts with at least one subunit (a2) and optionally at least one subunit (a1) - where the subunit (a1) can be different from that / those in the starting block or can be arranged in a different order compared to those in the starting block - to attach a new block containing parts from the subunits for (co)polymerization to the uncapped side of the starting block, thereby obtaining a diblock structure of [capping group]-[subunit (a1)]-[subunit (a2)], or [capping group]-[subunit (a1)]-[random-{subunit (a2)-subunit (a1)}];

[0136] Where, in the oligomers or polymers employed, there are already present more than one subunit (a1) and / or more than one subunit (a2), those subunits can be arranged in any order within such employed oligomers or polymers, and

[0137] where, in the case of the presence of more than one subunit (a1) and / or more than one subunit (a2) for polymerization, those subunits (and optionally oligomers / polymers, if employed) can be arranged in any order within the resulting main chain,

[0138] and where - optionally - at least one starting molecule is incorporated into the main chain structure.

[0139] The polymer main chain (A) and specifically (A1), (A2) and (A3) can optionally be capped at the end groups, the capping being carried out by known techniques with C1-C25 alkyl groups, preferably C1 to C4-groups. Such capping will be carried out after the production of the main chain and can preferably be carried out before grafting.

[0140] In the case of (A4), capping on one end group is carried out before the condensation polymerization with subunit (a1) and / or subunit (a2), since only then can structure (A4) be obtained. In another more preferred method, the production of (A4) starts from a monohydric alcohol, which is then reacted with an alkylene oxide to obtain a "mono-capped" oligomer / polymer of subunit (a1) (with a hydroxyl group at the end of the oligo / polyalkylene oxide chain), which is then reacted with subunit (a2) to obtain (A4).

[0141] When preparing oligoalkylene oxides / polyalkylene oxides as the starting block, diols can be used as the starting molecules for preparing such oligoalkylene oxides / polyalkylene oxides, so that such oligomers / polymers of subunit (a1) can contain in their structure a moiety derived from such diols. Diols for such use and methods for preparing such oligoalkylene oxides / polyalkylene oxides containing diols in their structure are known. Typical diols are ethylene glycol, propylene glycol, etc. For this purpose, all commonly known diols can in principle be used.

[0142] In another preferred embodiment, the polymer main chain serving as the grafting matrix contains at least one subunit (a1) and at least one subunit (a2), where

[0143] (a1) is a unit containing a moiety - preferably consisting essentially thereof - derived from at least one alkylene oxide monomer and / or at least one polyalkylene oxide-polymer having two hydroxyl end groups, the alkylene oxide monomer being selected from the group of C2- to C10-alkylene oxides, preferably C2 to C5-alkylene oxides,

[0144] (a2) is a unit containing at least one lactone and / or at least one hydroxy acid (preferably consisting thereof), and this seed unit (a2) is a moiety derived from a single lactone and / or hydroxy acid or an oligomeric or polymeric unit composed of at least one type of lactone and / or at least one type of hydroxy acid,

[0145] wherein preferably the at least one lactone and / or hydroxy acid is selected from group i) and / or ii), where

[0146] i) lactones, i.e., cyclic esters, starting with α-lactones (three ring atoms), followed by β-lactones (four ring atoms), γ-lactones (five ring atoms), etc.; such lactones are preferably β-propiolactone, γ-butyrolactone, δ-valerolactone, γ-valerolactone, ε-caprolactone, δ-decalactone, γ-decalactone, ε-decalactone; preferably caprolactone;

[0147] and

[0148] ii) hydroxy acids, which can be derived by hydrolysis from any lactone, especially from any lactone within the previous group i), especially α-, β- or γ-hydroxy acids derived by hydrolysis from the corresponding lactone, as well as lactic acid, glycolic acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 12-hydroxystearic acid, citric acid;

[0149] preferably lactic acid or caprolactone, more preferably caprolactone,

[0150] wherein the polymer backbone (A) as the grafting matrix,

[0151] the polymer backbone is selected from

[0152] (A1) a backbone composed of randomly arranged monomers, oligomeric and / or polymeric (a1)-subunits and monomers, oligomeric and / or polymeric (a2)-subunits, wherein there are more than one subunit (a1) and / or more than one subunit (a2);

[0153] (A2) a backbone composed of oligomeric or polymeric subunits (a2) as internal blocks and two external blocks of oligomeric and / or polymeric (a1)-subunits, which is defined as “-[(block of (a1))]-[(block of (a2))]-[(block of (a1))]-”, and may also contain higher-order block polymers such as pentablock, heptablock and nonablock, etc., wherein additional blocks of (a1) and (a2) are connected at the outside of the triblock structure, such as the pentablock “[(block of (a1))]-[(block of (a2))]-[(block of (a1))]-[(block of (a2))]-[(block of (a1))]-[(block of (a2))]-[(block of (a1))]” etc.;

[0154] (A3) A main chain composed of an internal block of oligomeric and / or polymeric (a1)-subunits and two outer blocks of oligomeric or polymeric subunits (a2), which is at least in the form of a triblock polymer defined as “-[block of (a2)]-[block of (a1)]-[block of (a2)]-”; and

[0155] (A4) A main chain composed of:

[0156] A first block having

[0157] (i) A capping group at one end - such a capping group is attached to the C1 - C18, preferably C1 - C4 - alkyl of the first block via an ether functional group; and

[0158] (ii) Oligomeric or polymeric subunits (a1); and

[0159] A second block attached to the first block at the opposite end of the first block (opposite to the capping on the first block) via an ether or ester functional group, the second block being composed of at least one subunit (a2) and optionally at least one subunit (a1),

[0160] wherein the optional subunit (a1) in the second block may be different from that / those in the first block, or may be arranged in a different order compared to those in the first block, and the order of subunits (A1) and (a2) may also be in any order, including a random structure,

[0161] Such a diblock structure has the following as the idealized structure when only using subunit (a2) for the second block: [capping group]-[subunit (a1)]-[subunit (a2)]

[0162] Or has the following as the idealized structure when using subunits (a1) and (a2) for the second block:

[0163] [capping group]-[subunit (a1)]-[random-{subunit (a2)-subunit (a1)};

[0164] And wherein - optionally - at least one initiator molecule is included in the main chain structure.

[0165] In a preferred embodiment, the polymer main chain (A) and specifically (A1), (A2) and (A3) are not capped at the chain ends but carry hydroxyl groups.

[0166] Preferably, the polyalkoxylate - ester main chain contains moieties derived from

[0167] (i) An alkylene oxide (AO) which comprises at least one of ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO), preferably at least one of EO and PO,

[0168] wherein the amount of the AO is 40 wt% to 95 wt%, preferably up to 90 wt%, and preferably 50 wt%, more preferably 60 wt% and even more preferably 70 wt%, and any value and range therebetween, each based on the total weight of the main chain,

[0169] the amount of EO is 0 wt.% to 100 wt.%, preferably 10 wt.%, more preferably 20 wt.%, even more preferably 30 wt.%, even more preferably 40 wt.%, such as 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.% or even 90 wt%, based on the total AO,

[0170] the total amount of the PO and / or BO is each 0 wt.% to 100 wt.%, preferably up to 90 wt.%, more preferably up to 80 wt.%, even more preferably up to 70 wt.%, even more preferably up to 60 wt.% and most preferably up to 50 wt.%, and any value therebetween, such as up to 5 wt.%, 10 wt.%, 15 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 55 wt.%, 65 wt.%, 75 wt.%, 85 wt.% or up to 95 wt.%, and more preferably 10 wt.%, even more preferably 20 wt.%, even further more preferably 30 wt.%, such as 40 wt.%, 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.% or even 90 wt%, each based on the total weight of the AO, wherein for the sum of PO and BO, the total amount of PO and BO totals 100 wt.%,

[0171] wherein the total amount of the AO totals 100 wt.%;

[0172] (ii) A lactone / hydroxy acid monomer, the amount of which is 1 wt.% and up to 60 wt.%, preferably up to 50 wt.%, more preferably up to 40 wt.%, most preferably up to 30 wt.%, and preferably 2 wt.%, more preferably 3 wt.%, even more preferably 4 wt.% and most preferably 5 wt.%, each based on the total weight of the main chain, preferably only caprolactone;

[0173] wherein the total weight of the sum of the subunits (a1) and (a2) in the main chain (A) totals 100 wt%.

[0174] More preferably, the amount of EO is at least 80 wt%, preferably at least about 85 wt%, more preferably at least about 90 wt%, even more preferably at least about 95% and most preferably about 100 wt.%, based on the total AO; the amount of PO and / or BO is each from about 0 wt.% to 50 wt.%, more preferably at most about 30 wt.%, even more preferably at most about 20%, even more preferably about 10 wt.% and most preferably about 0 wt.%, each based on the total weight of AO, based on the total AO; in a more preferred embodiment, the amounts of PO and BO given prior to this paragraph are for the total amount of the sum of PO and BO. In an even more preferred embodiment, the main-chain unit (a1) is made only of ethylene oxide.

[0175] In an alternative but preferred embodiment, at least two different alkylene oxides are used for preparing the main chain / present in the main chain.

[0176] Thus, in a more preferred embodiment, the polymer main chain consists of

[0177] (i) alkylene oxide (AO), which is selected from ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO), preferably only EO and PO,

[0178] The amount of EO is from 10 wt% to 90 wt%, preferably from 20 wt% to 80 wt%, more preferably from 30 wt% to 70 wt% and most preferably from 40 wt% to 60 wt%, based on the total AO,

[0179] The total amount of PO and BO is from 10 wt% to 90 wt%, preferably from 20 wt% to 80 wt%, more preferably from 30 wt% to 70 wt% and most preferably from 40 wt% to 60 wt%, each based on the total weight of AO, wherein for the sum of PO and BO, the total amount of PO and BO totals 100 wt.%, and

[0180] wherein the total amount of AO totals 100 wt.%;

[0181] (ii) the amount of lactone / hydroxy acid monomer is from 1 wt% and up to 60 wt%, preferably up to 40 wt%, more preferably up to 30 wt%, even more preferably up to 25 wt%, even further more preferably up to 20 wt% and most preferably up to 15 wt%, and preferably 2 wt%, more preferably 3 wt%, even more preferably 4 wt% and most preferably 5 wt%, each based on the total weight of the main chain, preferably only caprolactone;

[0182] wherein the total weight of the sum of the subunit (a1) and the subunit (a2) in the main chain (A) totals 100 wt%,

[0183] and wherein in the case of (A1), (A2) and (A3), the use of starting molecules is optional.

[0184] Thus, in a more preferred alternative embodiment, the polymer backbone consists of

[0185] (i) alkylene oxide (AO) is selected from ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO), preferably only EO and PO, more preferably only EO

[0186] the amount of EO is 20 wt% to 100 wt% based on the total AO,

[0187] the total amount of PO and BO is 0 wt.% to 80 wt.%, preferably up to 50 wt.%, more preferably up to 30 wt.%, even more preferably up to 20 wt.% and even further preferably up to 10 wt.% and most preferably zero, such as 45 wt.%, 45 wt.%, 45 wt.%, 25 wt.%, 15 wt.%, 7 wt.% and 5 wt.%, and any value therebetween, each based on the total weight of AO, wherein for the sum of PO and BO, the total amount of PO and BO totals 100 wt.%,

[0188] wherein the total amount of AO totals 100 wt.%;

[0189] (ii) the amount of lactone / hydroxy acid monomer is 5 wt% and up to 50 wt%, preferably up to 40 wt%, more preferably up to 35 wt% and even more preferably up to 30 wt% based on the total weight of the backbone, and as a lower limit preferably 7 wt%, more preferably 10 wt%, even more preferably 12 wt% and most preferably 15 wt%, such as 6 wt%, 8 wt%, 9 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt% and 15 wt% and any value therebetween as the lower limit and such as 30 wt%, 33 wt%, 37 wt%, 45 wt% and any value therebetween as the upper limit, preferably only caprolactone;

[0190] wherein the total weight of the sum of subunit (a1) and subunit (a2) in backbone (A) totals 100 wt%,

[0191] and wherein in the case of (A1), (A2) and (A3), the use of starting molecules is optional.

[0192] In an even more preferred embodiment, the backbone for any embodiment of the graft polymer of the invention as defined herein is a structure selected from structures (A1), (A2), (A3) and / or (A4).

[0193] Second structural unit of the graft polymer

[0194] Method is a polymer side chain (B) grafted onto a polymer backbone (A), wherein the polymer side chain (B) is obtainable by (co)polymerization of at least one vinyl ester monomer (B1), optionally a nitrogen-containing monomer (B2), optionally further monomers (B3), and optionally further monomers other than (B1), (B2), and (B3).

[0195] As the vinyl ester monomer (B1), at least one of vinyl acetate, vinyl propionate, and / or vinyl laurate is selected. In addition to those, further vinyl ester monomers (B1) known to those skilled in the art, such as vinyl valerate, vinyl pivalate, vinyl neodecanoate, vinyl caprate, and / or vinyl benzoate, can be employed.

[0196] As the optional monomer (B2), at least one nitrogen-containing monomer selected from the group consisting of: vinyl lactams, vinyl imidazoles, 1-vinyltriazoles, 4-vinylpyridines, 4-vinylpyridine-N-oxides, 2-vinylpyridines, 1-vinyl oxazolidinones, N-vinylformamides, N-vinylacetamides, N-vinyl-N-methylacetamides, and acrylamides, such as acrylamide, methacrylamide, N-alkyl-substituted acrylamides, N,N'-dialkyl(meth)acrylamides; mono- and dialkylamino-alkyl-(meth)acrylates, which are preferably vinyl lactam monomers and / or vinyl imidazole monomers, more preferably the vinyl lactam is selected from N-vinyl lactams, such as N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, even more preferably N-vinylpyrrolidone, N-vinylcaprolactam, and most preferably N-vinylpyrrolidone, and the vinyl imidazole is preferably N-vinylimidazole, 2-methyl-1-imidazole, more preferably N-vinylimidazole.

[0197] Further monomers (B3) can be employed as optional monomers, such monomers being different from (B1) and (B2) and being present in an amount of less than 10% of the total amount of monomers preferably used to obtain the polymer side chain (B), and more preferably being present only as impurities rather than being intentionally added for polymerization. The (B3) monomer can be any monomer selected from the following: 1-vinyl oxazolidinone and other vinyl oxazolidinones, 4-vinylpyridine-N-oxide, N-vinylformamide and its amines (if hydrolyzed after polymerization), N-vinylacetamide, N-vinyl-N-methylacetamide, alkyl esters of (meth)acrylic acid and their derivatives.

[0198] In addition to the monomers (B1), (B2) and (B3), at least one additional monomer (different from the previous ones) may be present for copolymerization to produce the side chain (B), where such additional monomer is present only in an amount of less than 2% of the total amount of monomers used to obtain the polymer side chain (B), and preferably is present only as an impurity and not intentionally added for polymerization.

[0199] In the presence of the monomer (B2), based on the total weight of the graft polymer, the amounts of the monomers are as follows:

[0200] (B) is 10% to 60%, preferably up to 50%, more preferably up to 40% and preferably 20%;

[0201] Based on the total weight of the graft polymer in weight percentage, (B1) (vinyl ester) is 9% to 55%, preferably up to 50%, more preferably up to 40%, even more preferably up to 35% and even more preferably up to 30%;

[0202] Based on the total weight of the graft polymer in weight percentage, (B2) (nitrogen-containing monomer) is 1% to 41%, preferably up to 30%, more preferably up to 25%, such as 1% to 25% and more preferably 5% to 25%, even more preferably up to 15%, such as 1% to 15% and more preferably 5% to 15%, and further such as up to 10% to 40%, 35%, 20%, 10%, and each number between 1% and 41%, where preferably the amount of (B2) is not higher than the amount of (B1);

[0203] (B3) (additional monomer) is 0% to 10%, preferably at most 2%, more preferably at most 1%, even more preferably about 0%, but in all cases at most 10% of the amount of (B1), and does not exceed the amount of (B2).

[0204] The amount of the additional monomer other than (B1), (B2) and (B3) is as detailed previously.

[0205] In the absence of the monomer (B2), based on the total weight of the graft polymer, the amounts of the monomers are as follows:

[0206] (B) is 5% to 60%, preferably up to 50% and preferably 20%;

[0207] Based on the total weight of the graft polymer in weight percentage, (B1) (vinyl ester) is the total amount of (B) minus the total amount of (B3);

[0208] (B2) (nitrogen-containing monomer) is 0%;

[0209] (B3) (Additional monomer) is from 0 to 10, preferably at most 2, more preferably at most 1, and even more preferably about 0.

[0210] The amount of additional monomers other than (B1), (B2) and (B3) is as detailed previously.

[0211] In a preferred embodiment, the amount of the vinyl ester monomer (B1) is generally not less than 10% by weight (relative to the sum of (B1) and (B2)).

[0212] Preferably, the optional additional monomer (B3) is present only as an impurity and not intentionally added for polymerization. More preferably, the amount is less than 1% by weight, more preferably less than 0.5% by weight, even more preferably less than 0.01% by weight, based on the total weight of the monomer (B1), and most preferably such monomer (B3) is substantially absent, and most preferably even completely absent any other monomers other than the monomer (B1) and the optional monomer (B2). This also applies to additional monomers other than (B1), (B2) and (B3).

[0213] In a preferred embodiment, the graft polymer of the present invention comprises a polymer side chain (B) obtained or obtainable by radical polymerization of the at least one vinyl ester monomer (B1) and optionally at least one other monomer (B2) and optionally at least one additional monomer (B3) in the presence of a polymer backbone (A).

[0214] Wherein at least 10 weight percent of the total amount of the vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably selected from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of the vinyl ester can be any other known vinyl ester, wherein preferably at least 80, more preferably at least 90 weight percent and most preferably substantially only vinyl acetate is used as the vinyl ester (weight percent based on the total weight of the vinyl ester monomer B1 employed).

[0215] In an even more preferred embodiment of the previous embodiment, substantially no other monomer (B3) is employed.

[0216] In an even more preferred embodiment of the previous embodiment, substantially no other monomers (B2) and (B3) are employed.

[0217] In a preferred embodiment, the graft polymer of the present invention consists of monomers, wherein

[0218] (B) These monomers are:

[0219] (B1) At least one vinyl ester selected from vinyl acetate, vinyl propionate, and / or vinyl laurate, in an amount of 70% to 100% by weight, preferably only vinyl acetate, based on the total weight of the monomers grafted onto the main chain (A), and

[0220] (B2) Optionally at least one nitrogen-containing monomer, in an amount of 0% to 30% by weight based on the total amount of the monomers grafted onto the main chain (A), which is preferably an N-vinyl lactam such as N-vinyl pyrrolidone, N-vinyl piperidone, N-vinyl caprolactam, even more preferably N-vinyl pyrrolidone and / or N-vinyl caprolactam, and most preferably N-vinyl pyrrolidone,

[0221] wherein the vinyl ester monomer (B1) is optionally partially or completely hydrolyzed after polymerization.

[0222] In its preferred embodiment, the vinyl ester is not hydrolyzed.

[0223] In an alternative embodiment, in addition to at least one monomer (B1), there is also at least one vinyl lactam, preferably vinyl pyrrolidone and / or vinyl caprolactam, more preferably only vinyl pyrrolidone, as monomer (B2), wherein monomer (B1) preferably comprises vinyl acetate, and even more preferably is only vinyl acetate. Even more preferably, vinyl acetate is the only monomer (B1) and vinyl pyrrolidone is the only monomer (B2).

[0224] In an alternative embodiment of the embodiment in the immediately preceding paragraph, the monomer (B1) can be partially or completely hydrolyzed after the polymerization reaction. In its preferred embodiment, the monomer (B1) is partially hydrolyzed, and even more preferably hydrolyzed to up to 80, 70 or 60, 50, 40, 30, 20 or 10 mole percent based on the total amount of monomer (B1).

[0225] Preferably, the monomer (B1) is partially hydrolyzed to 20%, and hydrolyzed to up to 50%. In the most preferred embodiment of the previous embodiment, vinyl acetate is used as monomer (B1) and vinyl pyrrolidone is used as monomer (B2), and the polymer portion derived from vinyl acetate is preferably partially hydrolyzed in an amount of about 20 mole% to 50 mole%, more preferably about 30 mole% to 45 mole%, such as about 40 mole%, based on the total amount of vinyl acetate, after polymerization.

[0226] In an alternative, even more preferred embodiment of the immediately preceding two paragraphs, the vinyl ester is not hydrolyzed at all.

[0227] It should be understood that the amounts of (A), (B), (B1), (B2), (B3) and additional monomers other than the previous monomers can be selected from the various detailed ranges given independently, i.e., the lower and upper boundaries can also be combined from two different ranges given for one aspect to produce a numerical range not explicitly specified by numbers. However, such combined ranges for, for example, (A), (B), (B1), (B2) and (B3) are explicitly intended to be covered in the present invention.

[0228] Moreover, in one embodiment of the present invention, a wide range and a very particularly preferred narrow range can be combined, where the selection of the range of one component is made independently of the selection of the range of the other component, as long as the total sum is "100% - polymer": for example, the most preferred ranges of (A) and (B) can be selected and combined with the widest possible range given for (B1) / (B2) / (B3) and any other possible combinations.

[0229] Preferably, for all the selections that can be made for (A) / (B) and (B1) / (B2) / (B3), the same selection is made, for example, all "preferred" ranges are selected, or - more preferably - all "more preferred" ranges are selected, or - most preferably - all "most preferred" ranges are selected.

[0230] The graft polymer of the present invention as detailed previously has a polydispersity (PDI) Mw / Mn of at most 10, preferably at most 5, more preferably at most 3 and most preferably in the range of 1.0 to 2.6, as well as any numerical value a as an upper or lower limit value and any range therebetween, such as 1.3 to 2.6, 1 to 3, etc. (where Mw = weight-average molecular weight in g / mol and Mn = number-average molecular weight in g / mol; where PDI is dimensionless), where lower values are preferred, but this depends on the Mn of the polymer backbone used (the higher the Mn of (A), typically the higher the PDI) and also the amount of (B) (the higher the amount of (B) relative to the amount of (A), typically the higher the PDI).

[0231] M w and M n The corresponding values of and can be determined using GPC standard methods (such as the methods referred to in the experimental section). However, it is also possible to calculate the molecular weight of the backbone used in the present invention because those reactions proceed substantially to completion. Therefore, calculating the molecular weight based on the total molar amount of the components used in the preparation reaction is also a feasible way.

[0232] The graft polymer of the present invention may contain a certain amount of ungrafted polymer ("ungrafted side chains"), which is made from monomers that have not reacted with the polymer backbone (i.e., grafted (onto the polymer backbone) to the polymer backbone).

[0233] The amount of such ungrafted polymer can be high or low, depending on the reaction conditions, but is preferably reduced and thus more preferably 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 and relative amounts of the monomer and free radical initiator, and is also related to the amount of the backbone present. Such adjustment is in principle known to those skilled in the art and is described in detail below for the present invention in the description of the method for obtaining the graft polymer of the present invention.

[0234] It has been found that the graft polymer of the present invention, as detailed previously herein, exhibits improved biodegradability, which is at least 35, more preferably at least 40, even more preferably at least 50, such as 41, 42, 43, 44, 45, etc., 51, 52, 53, etc., 55, 60, 65, etc. and any value therebetween and up to 100% when tested according to OECD 301F within 28 days.

[0235] The ratio of (A) to (B) used in the examples herein is:

[0236] (A) 20% to 95%, preferably 30% to 90%, more preferably 40% to 85%, most preferably 50% to 80% of the polymer backbone as the graft matrix, and

[0237] (B) 5% to 80%, preferably 10% to 70%, more preferably 15% to 60%, most preferably 20% to 50% of the polymer side chain (B) grafted onto the polymer backbone (A),

[0238] where each percentage is based on the total weight of the graft polymer, and the sum of (a) plus (B) is 100 wt.%.

[0239] Sub-units (a1), (a2), polymer backbones (A), (A1), (A2), (A3) and (A4) as graft matrices as defined by their structure or their preparation, and monomers (B), (B1), (B2), (B3), and any one and each of the additional monomers other than (B1), (B2), (B3) are those as defined herein and specifically those defined previously in all of its embodiments, preferred embodiments, etc. and in the examples; for sub-units (a1), (a2), polymer backbones (A), (A1), (A2), (A3) and (A4) as graft matrices as defined by their structure or their preparation, and monomers (B), (B1), (B2), (B3), and any such embodiment of the additional monomers other than (B1), (B2), (B3) can be selected and combined individually, provided that such selection is possible and not excluded herein, i.e., the sum needs to be totaled as required and the embodiments are compatible (i.e., an embodiment requiring (B2) is clearly not combined with an embodiment requiring the absence of (B)).

[0240] In a more preferred embodiment, the graft polymer of the present invention and / or as detailed previously

[0241] consists of:

[0242] (A) at least one polymer backbone as a graft matrix, such graft matrix being any of the previously defined polymer backbones in any embodiment, preferably any one of (a1), (A2), (A3) and (A4) as defined previously

[0243] in an amount as defined in any embodiment herein

[0244] including the specification, examples and claims

[0245] and

[0246] (B) a polymer side chain (B) grafted onto the polymer backbone (A), wherein the polymer side chain (B) is obtainable by the (co)polymerization of at least one vinyl ester monomer (B1), optionally a nitrogen-containing monomer (B2) and optionally additional monomers (B3) and optionally additional monomers

[0247] all such monomers being any monomers as defined in any embodiment herein

[0248] in an amount as defined in any embodiment herein

[0249] including the specification, examples and claims.

[0250] In one embodiment of the previous embodiment, the vinyl ester monomer is vinyl acetate as the sole monomer (B1), and more preferably vinyl pyrrolidone is the sole monomer (B2), and most preferably there are no other monomers (B3) and no additional monomers other than the previous monomers.

[0251] In a preferred embodiment of the previous embodiment, the vinyl ester is hydrolyzed to about 20 to 50 mole percent, preferably about 30 mole % to 45 mole %, and most preferably about 40 mole %.

[0252] In a specific embodiment, the graft polymer of the present invention consists of:

[0253] (A) 20% to 95%, preferably 30% to 90%, more preferably 40% to 85%, and most preferably 50% to 80% of a polymer backbone as the graft matrix, where the percentages are by weight relative to the total weight of the graft polymer;

[0254] The polymer backbone contains at least one subunit (a1) and at least one subunit (a2), where

[0255] (a1) is a unit containing a moiety - preferably consisting essentially of - derived from at least one alkylene oxide monomer and / or at least one polyalkylene oxide - polymer having two hydroxyl end groups, the alkylene oxide monomer being selected from the group of C2 - to C10 - alkylene oxides, preferably C2 to C5 - alkylene oxides,

[0256] (a2) is a unit containing at least one lactone and / or at least one hydroxy acid (preferably consisting of), this subunit (a2) being a moiety derived from a single lactone and / or hydroxy acid or an oligomeric or polymeric unit consisting of at least one type of lactone and / or at least one type of hydroxy acid,

[0257] where preferably the at least one lactone and / or hydroxy acid is selected from group i) and / or ii), where

[0258] i) lactones, i.e., cyclic esters, starting with α - lactones (three ring atoms), followed by β - lactones (four ring atoms), γ - lactones (five ring atoms), etc.; such lactones are preferably β - propiolactone, γ - butyrolactone, δ - valerolactone, γ - valerolactone, ε - caprolactone, δ - decanolide, γ - decanolide, ε - decanolide; preferably caprolactone;

[0259] And

[0260] (ii) Hydroxy acids, which can be derived by hydrolysis from any lactone, especially any lactone within the previous group i), especially α-, β- or γ-hydroxy acids derived by hydrolysis from the corresponding lactone, and lactic acid, glycolic acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 12-hydroxystearic acid, citric acid;

[0261] Preferably lactic acid or caprolactone, more preferably caprolactone,

[0262] wherein the polymer backbone

[0263] is obtained by any of the following

[0264] (A1) Copolymerization of at least one subunit (a1) and at least one subunit (a2), where optionally at least one oligomer or polymer made from at least one subunit (a1) or at least one subunit (a2) can also be used in the copolymerization of the at least one subunit (a1) and the at least one subunit (a2);

[0265] (A2) First oligomerize / polymerize the subunit (a2), and then polymerize the product with the subunit (a1);

[0266] (A3) First oligomerize / polymerize the subunit (a1), and then copolymerize the product with the subunit (a2); or

[0267] (A4) First provide an oligomeric or polymeric subunit (a1) capped on one side, preferably etherified with an alcohol, more preferably a short-chain alcohol C1 to C4, which - as a starting block - thereafter reacts with at least one subunit (a2) and optionally at least one subunit (a1) - where the subunit (a1) can be different from that / those in the starting block or can be arranged in a different order compared to those in the starting block - to attach a new block containing parts from the subunits for (co)polymerization to the uncapped side of the starting block, thereby obtaining a diblock structure of [capping group]-[subunit (a1)]-[subunit (a2)], or [capping group]-[subunit (a1)]-[random-{subunit (a2)-subunit (a1)}];

[0268] where in the case where more than one subunit (a1) and / or more than one subunit (a2) already exist in the oligomer or polymer used, those subunits can be arranged in any order within such an oligomer or polymer used, and

[0269] where in the case where more than one subunit (a1) and / or more than one subunit (a2) are used for polymerization, those subunits (and optionally the oligomer / polymer, if used) can be arranged in any order within the obtained backbone;

[0270] or selected from

[0271] (A1) a main chain composed of randomly arranged monomeric, oligomeric, and / or polymeric (a1)-subunits and monomeric, oligomeric, and / or polymeric (a2)-subunits, where there are more than one subunit (a1) and / or more than one subunit (a2);

[0272] (A2) a main chain composed of an oligomeric or polymeric subunit (a2) as an internal block and two outer blocks of oligomeric and / or polymeric (a1)-subunits, which is defined as "-[block of (a1)]-[block of (a2)]-[block of (a1)]-", and may also contain higher-order block polymers such as pentablock, heptablock, and nonablock, etc., where additional blocks of (a1) and (a2) are connected at the outside of the triblock structure, such as the pentablock "[block of (a1)]-[block of (a2)]-[block of (a1)]-[block of (a2)]-[block of (a1)]-[block of (a2)]-[block of (a1)]", etc.;

[0273] (A3) a main chain composed of an internal block of oligomeric and / or polymeric (a1)-subunits and two outer blocks of oligomeric or polymeric subunit (a2), which is at least in the form of a triblock polymer defined as "-[block of (a2)]-[block of (a1)]-[block of (a2)]-"; and

[0274] (A4) a main chain composed of:

[0275] a first block having

[0276] (i) a capping group at one end - such a capping group is attached to the C1 to C18, preferably C1-C4-alkyl of the first block via an ether functional group; and

[0277] (ii) an oligomeric or polymeric subunit (a1); and

[0278] a second block attached to the first block at the opposite end of the first block (opposite to the capping group on the first block) via an ether or ester functional group, the second block being composed of at least one subunit (a2) and optionally at least one subunit (a1), where the optional subunit (a1) in the second block may be different from that / those in the first block, or may be arranged in a different order compared to those in the first block, and the order of these subunits (A1) and (a2) may also be in any order, including a random structure,

[0279] This diblock structure has the following items as the idealized structure when only subunit (a2) is used for the second block:

[0280] [End group]-[Subunit (a1)]-[Subunit (a2)]

[0281] Or when subunits (a1) and (a2) are used for the second block, it has the following items as the idealized structure:

[0282] [End group]-[Subunit (a1)]-[Random-{subunit (a2)-subunit (a1)}];

[0283] Wherein the amounts of subunits (a1) and (a2) are those as defined previously herein;

[0284] And wherein - optionally - at least one initiator molecule is included in the main chain structure;

[0285] And

[0286] (B) 5% to 80%, preferably 10% to 70%, more preferably 15% to 60%, most preferably 20% to 50% of polymer side chains (B) grafted onto the polymer main chain (A), wherein the polymer side chains (B) are obtainable by the (co)polymerization of at least one vinyl ester monomer (B1), optionally a nitrogen-containing monomer (B2), and optionally additional monomers (B3) and optionally additional monomers,

[0287] Wherein the percentages are by weight relative to the total weight of the graft polymer;

[0288] Wherein these monomers are:

[0289] (B1) At least one vinyl ester selected from vinyl acetate, vinyl propionate, and / or vinyl laurate and any other vinyl esters known to those skilled in the art, such as vinyl valerate, vinyl pivalate, vinyl neodecanoate, vinyl decanoate, and / or vinyl benzoate;

[0290] Optionally

[0291] (B2) At least one nitrogen-containing monomer selected from the group consisting of: vinyl lactams, vinyl imidazoles, 1-vinyl triazoles, 4-vinyl pyridine, 4-vinyl pyridine-N-oxide, 2-vinyl pyridine, 1-vinyl oxazolidinone, N-vinyl formamide, N-vinyl acetamide, N-vinyl-N-methyl acetamide, and acrylamides such as acrylamide, methacrylamide, N-alkyl-substituted acrylamides, N,N'-dialkyl(methyl)acrylamides; mono- and dialkylamino-alkyl-(meth)acrylates, preferably vinyl lactam monomers and / or vinyl imidazole monomers, more preferably the vinyl lactam is selected from N-vinyl lactams such as N-vinyl pyrrolidone, N-vinyl piperidone, N-vinyl caprolactam, even more preferably N-vinyl pyrrolidone, N-vinyl caprolactam, and most preferably N-vinyl pyrrolidone, and the vinyl imidazole is preferably N-vinyl imidazole, 2-methyl-1-imidazole, more preferably N-vinyl imidazole;

[0292] Optionally

[0293] (B3) At least one additional monomer such as 1-vinyl oxazolidinone and other vinyl oxazolidinones, 4-vinyl pyridine-N-oxide, N-vinyl formamide and its amine - if hydrolyzed after polymerization, N-vinyl acetamide, N-vinyl-N-methyl acetamide, any one or more of the alkyl esters of (meth)acrylic acid; and

[0294] Optionally

[0295] At least one additional monomer different from the previous ones, such other monomer being present in an amount of less than 2% of the total amount of monomers used to obtain the polymer side chain (B), and preferably being present only as an impurity rather than being intentionally added for polymerization;

[0296] wherein the amounts are preferably as follows:

[0297] - if (B2) is present -

[0298] (B) is 10% to 60%, preferably up to 50%, more preferably up to 40% and preferably 20%;

[0299] Based on the total weight of the graft polymer in weight percentage, (B1) (vinyl ester) is

[0300] 9% to 55%, preferably up to 50%, more preferably up to 40%, even more preferably up to 35% and even more preferably up to 30%;

[0301] Based on the total weight of the graft polymer in weight percent, (B2) (nitrogen-containing monomer) is 1% to 41%, preferably up to 30%, more preferably up to 25%, such as 1% to 25% and more preferably 5% to 25%, even more preferably up to 15%, such as 1% to 15% and more preferably 5% to 15%, and further such as up to 10% to 40%, 35%, 20%, 10%, and each number between 1% and 41%, wherein preferably the amount of (B2) is not higher than the amount of (B1).

[0302] or

[0303] -if (B2) is absent-

[0304] (B) is 5% to 60%, preferably up to 50% and preferably 20%;

[0305] Based on the total weight of the graft polymer in weight percent, (B1) (vinyl ester) is the total amount of (B) minus the total amount of (B3).

[0306] (B2) (nitrogen-containing monomer) is 0%.

[0307] And further on the premise that in all previous cases

[0308] (B3) (additional monomer) is 0% to 10%, preferably at most 2%, more preferably at most 1%, even more preferably about 0%, but in all cases at most 10% of the amount of (B1), and does not exceed the amount of (B2);

[0309] Wherein preferably at least 10 weight percent of the total amount of vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably selected from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of vinyl ester can be any other known vinyl ester, wherein preferably at least 80, more preferably at least 90 weight percent and most preferably substantially only vinyl acetate is used as the vinyl ester (weight percent based on the total weight of the vinyl ester monomer B1 employed).

[0310] And optionally hydrolyze the vinyl ester after polymerization.

[0311] In one embodiment of the previous embodiment, the vinyl ester monomer is vinyl acetate as the only monomer (B1), and more preferably vinyl pyrrolidone is the only monomer (B2), and most preferably there are no other monomers (B3) and additional monomers other than the previous monomers.

[0312] In a preferred embodiment of the previous embodiment, the vinyl ester is hydrolyzed to about 20 to 50 mole percent, preferably about 30 to 45 mole percent, and most preferably about 40 mole percent.

[0313] The polymers of the present invention preferably have at least one, preferably two or more of the following additional properties in order to be more successfully used in various application fields of the present invention:

[0314] i) The polymer backbone (A) can carry two hydroxyl groups as end groups or can be capped at both ends with C1 to C22-alkyl, preferably C1 to C4 alkyl;

[0315] ii) The graft polymer has a polydispersity (PDI) Mw / Mn of at most 10, preferably at most 5, more preferably at most 3 and most preferably in the range of 1.0 to 2.6, and any value a as an upper or lower limit value and any range therebetween, such as 1.3 to 2.6, 1 to 3, etc. (where Mw = weight average molecular weight and Mn = number average molecular weight [g / mol / g / mol]);

[0316] iii) The biodegradability of the graft polymer is at least 35%, more preferably at least 40%, even more preferably at least 45%, even further more preferably at least 50% within 28 days when tested according to OECD 301F, such as 46%, 47%, 48%, 49%, 50%, 55%, 60%, 65%, 70%, 75%, etc. and any value therebetween and up to 100%.

[0317] Furthermore, the graft polymer is preferably water-soluble to some extent in order to be able to use these polymers in an aqueous environment typically present in various application fields such as those of the present invention. Preferably, the polymers of the present invention should exhibit medium to good, more preferably good solubility in the environment of aqueous formulations, such as those typically used in various formulations, for example dishwashing, automatic dishwashing, hard surface cleaning, fabric cleaning, fabric care, cosmetic formulations, etc.

[0318] Furthermore, the graft polymer solution preferably has a viscosity such that the solid concentration of the polymer is rather high for handling during and after production and for providing to the user, and the polymer may be dissolved, for example, as a "pure" (then typically liquid) product in a solvent, typically an aqueous solution containing water and an organic solvent, water only, or an organic solvent only, and the viscosity of such a polymer or polymer solution is within a range that allows typical technical process steps such as casting, pumping, metering, etc. Thus, at a polymer concentration of preferably at least 10 wt.%, more preferably at least 20 wt.%, even more preferably at least 40 wt.%, and most preferably at least 50 wt.%, such as at least 60 wt.%, 70 wt.%, 80 wt.%, or even 90 wt.% (based on the total solid content of the polymer in the solution, as defined by the weight percentage of the dried polymer within the total weight of the polymer solution), the viscosity should preferably be in the range of up to less than 4000 mPas, more preferably up to 3500 mPas, even more preferably up to 3000 mPas, such as up to 4500, 3750, 3250, 2750, or even 2600 or below, such as 2500, 2000, 1750, 1500, 1250, 1000, 750, 500, 250, 200, 150, or 100 mPas. The viscosity can be measured at 25 °C or at an elevated temperature, for example, at a temperature of 50 °C or even 60 °C. In this way, the polymer solution can be properly handled on a commercial scale. Of course, it is obvious that depending on the amount of the solvent added, the viscosity is lower when the amount of the solvent increases and vice versa, thus allowing adjustment in the desired case. It is also obvious that the measured viscosity depends on the temperature at which it is measured. For example, when measured at a lower temperature, the viscosity of a given polymer with a given solid content of, for example, 80 wt.% will be higher, and when measured at a higher temperature, the viscosity will be lower. In a preferred embodiment, the solid content is between 70 wt.% and 99 wt.%, more preferably between 75 wt.% and 85 wt.%, and no additional solvent is added except for the polymer prepared. In a more preferred embodiment, when measured at 60 °C, the solid content is between 70 wt.% and 99 wt.%, more preferably between 75 wt.% and 95 wt.%, no additional solvent is added except for the polymer prepared, and the viscosity is lower than 3000 mPas, more preferably 3250, or even lower than 2750, 2600, 2500, 2000, 1750, 1500, 1250, 1000, 750, 500, or even 250 mPas. The viscosity can be determined as is commonly known for such polymers, preferably as described in the experimental section below.

[0319] Of course, as a further criterion, the individual properties of specific polymers need to be evaluated and thus each individual formulation in a specific field of application graded. Due to the broad usefulness of the polymers of the present invention, an exhaustive overview or detailed guidance for each field is not possible, but the present specification and examples give guidance on how to prepare and select available polymers with desired properties and how to adjust these properties to desired requirements. One such criterion in the field of home care and especially fabric care is of course the performance during washing, for example subjecting a certain material exhibiting certain material stains to a defined washing procedure.

[0320] These examples provide some guidance for the application of fabric washing (i.e., the general field of fabric care).

[0321] Depending on the individual requirements for polymers exhibiting defined degrees of biodegradability, water solubility and viscosity (i.e., processing properties), the general and specific teachings herein - not intended to be limited to the specific examples given - will guide on how to obtain such polymers.

[0322] Use

[0323] The present invention also encompasses a method for obtaining a graft polymer according to any of the previous embodiments as defined herein and specifically in any of the embodiments in the previous part but also in any of the examples disclosed herein, wherein at least one vinyl ester monomer (B1), optionally at least one nitrogen-containing monomer (B2), optionally further monomers (B3) and optional further monomers (other than (B1), (B2) and (B3)) are polymerized in the presence of at least one polymer backbone (A) as defined herein, preferably selected from the main chains (A1), (A2), (A3) and (A4) as defined herein, wherein the polymer side chain (B) is obtained by free radical polymerization, preferably by initiating free radical polymerization using a free radical forming compound,

[0324] wherein each of B1, B2 and B3 (and further monomers other than (B1), (B2) and (B3)) and (A), (A1), (A2), (A3) and (A4) are as defined hereinbefore in including the claims and including any of the embodiments as exemplified in the following examples, wherein each is preferably selected from any of its preferred option grades, provided that each can be individually selected from its preferred options, but always meeting the general requirements of compatibility of the preferred options, such as the sum not exceeding 100% etc.

[0325] It must be noted that the "grafting method" itself (wherein a polymer backbone, such as the polymer backbone (A) described above herein, is grafted with polymer side chains) is known to the person skilled in the art. Any method known to the person skilled in the art in this regard can in principle be used in the present invention.

[0326] Free radical polymerization itself is also known to the person skilled in the art. It is also known to this person that the process according to the invention can be carried out in the presence of a free radical forming initiator (C) and / or at least one solvent (D).

[0327] The person skilled in the art knows the suitable corresponding components per se.

[0328] The term "free radical polymerization" as used in the context of the present invention encompasses, in addition to free radical polymerization, its variants such as controlled free radical polymerization. Suitable control mechanisms are RAFT, NMP or ATRP, including suitable control agents, which are known per se to the person skilled in the art.

[0329] In a preferred embodiment, the process for producing the graft polymers according to the invention and / or as detailed previously comprises at least one vinyl ester monomer (B1) and optionally at least one nitrogen-containing monomer (B2), optionally at least one further monomer (B3) and optionally further monomers - the latter being preferably present only as impurities and more preferably being substantially absent - in the presence of at least one polymer backbone (A) preferably selected from the main chains (A1), (A2), (A3) and (A4) as defined previously herein, a free radical forming initiator (C) and (if desired) up to 50% by weight, based on the sum of components (A), (B) and (C), of at least one organic solvent (D) at an average polymerization temperature at which the initiator (C) has a decomposition half-life of 40 to 500 min, in such a way that the fractions of unreacted graft monomers (B1), optional (B2) and optional (B3) (the further monomers are typically not monitored as they are present only in low, thus negligible, amounts as impurities) and the initiator (C) in the reaction mixture remain continuously substoichiometric with respect to the copolymer backbone (A). In a preferred embodiment, monomer (B2) is not used. In a more preferred embodiment, neither monomer (B2) nor monomer (B3) is used. In an even more preferred embodiment, only monomer (B1) is used. Generally, the amount of further monomers other than (B1), (B2) and (B39) is minimized, preferably they are completely absent.

[0330] In a preferred embodiment of any embodiment of the method as detailed in the preceding paragraphs, at least 10 weight percent of the total amount of vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate, and vinyl laurate, more preferably selected from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of vinyl ester may be any other known vinyl ester, wherein preferably at least 60, more preferably at least 70, even more preferably at least 80, even more preferably at least 90 weight percent and most preferably substantially only (i.e., about 100 wt.% or even 100 wt.%) vinyl acetate is used as the vinyl ester (weight percent based on the total weight of vinyl ester monomer B1 employed).

[0331] Generally, in addition to monomers (B1), (B2), and (B3), at least one additional monomer (different from the previous ones) can be used for copolymerization to produce side chain (B), wherein such additional monomer is present only in an amount less than 2% of the total amount of monomers used to obtain polymer side chain (B), and preferably is employed only as - practically inevitable - impurities rather than being intentionally added for polymerization, and most preferably is not present at all.

[0332] In a more preferred embodiment of the previous two paragraphs, the following additional conditions 1) (presence of (B2)) and 2) (absence of (B2)) apply to the amounts and ratios of the monomers:

[0333] In the case of using monomer (B2), based on the total weight of the graft polymer, the amounts of the monomers are as follows:

[0334] (B) is 10% to 60%, preferably up to 50%, more preferably up to 40%, and preferably 20%;

[0335] Based on the total weight of the graft polymer in weight percent, (B1) (vinyl ester) is 9% to 55%, preferably up to 50%, more preferably up to 40%, even more preferably up to 35%, and even more preferably up to 30%;

[0336] Based on the total weight of the graft polymer in weight percent, (B2) (nitrogen-containing monomer) is 1% to 41%, preferably up to 30%, more preferably up to 25%, such as 1% to 25% and more preferably 5% to 25%, even more preferably up to 15%, such as 1% to 15% and more preferably 5% to 15%, and further such as up to 10% to 40%, 35%, 20%, 10%, and each number between 1% and 41%, wherein preferably the amount of (B2) is not higher than the amount of (B1);

[0337] (B3) (Additional monomer) is 0% to 10%, preferably at most 2%, more preferably at most 1%, even more preferably about 0%, but in all cases at most 10% of the amount of (B1) and not exceeding the amount of (B2).

[0338] The amount of additional monomers other than (B1), (B2) and (B3) is as detailed previously, and the monomers (B1), (B2) and (B3) are those as detailed in any of the embodiments disclosed hereinbefore.

[0339] In the case where monomer (B2) is not used, based on the total weight of the graft polymer, the amounts of the monomers are as follows:

[0340] B) is 5% to 60%, preferably up to 50% and preferably 20%;

[0341] Based on the total weight of the graft polymer in weight percentage, (B1) (vinyl ester) is the total amount of (B) minus the total amount of (B3).

[0342] (B2) (nitrogen-containing monomer) is 0%;

[0343] (B3) (additional monomer) is 0 to 10, preferably at most 2, more preferably at most 1, even more preferably about 0.

[0344] The amount of additional monomers other than (B1), (B2) and (B3) is as detailed previously, and the monomers (B1), (B2) and (B3) are those as detailed in any of the embodiments disclosed hereinbefore.

[0345] In a preferred embodiment, the amount of the vinyl ester monomer (B1) used is generally not less than 10% by weight (relative to the sum of (B1) and (B2)).

[0346] Preferably, the optional additional monomer (B3) is also present only as an impurity and not intentionally added for polymerization. More preferably, the amount is less than 1% by weight, more preferably less than 0.5% by weight, even more preferably less than 0.01% by weight based on the total weight of monomer (B1). Most preferably, such monomer (B3) is substantially absent, and most preferably even no other monomers are present except monomer (B1) and the optional monomer (B2). This also applies to additional monomers other than (B1), (B2) and (B3).

[0347] In a particularly preferred embodiment, based on the total weight of the graft polymer, the amounts of the monomers used are as follows:

[0348] (A) is 40% to 90%, preferably 50%, more preferably 60% and preferably at most 80% of the polymer backbone as defined previously herein, preferably at least one of (A1), (A2) and (A3), as the grafting matrix,

[0349] (B) is 10% to 60%, preferably up to 50%, more preferably up to 40% and preferably 20%;

[0350] (B1) (vinyl ester) is 9% to 55%, preferably up to 50%, more preferably up to 40%, even more preferably up to 35% and even more preferably up to 30%;

[0351] (B2) (at least one vinyl lactam, preferably vinyl pyrrolidone and / or vinyl caprolactam, more preferably vinyl pyrrolidone) is 1% to 25%, preferably up to 20%, more preferably up to 15%, even more preferably up to 10%, such as even only up to 5%, where the amount of (B2) is at most not higher than the amount of (B1);

[0352] (B3) (additional monomer) is 0% to 2%, preferably at most 1%, more preferably 0%, but in all cases at most 10% of the amount of (B1), and does not exceed the amount of (B2);

[0353] More preferably, the optional additional monomer (B3) and additional monomers other than (B1), (B2) and (B3) are preferably present only as impurities and not intentionally added for polymerization; more preferably, the amount is less than 1% by weight, more preferably less than 0.5% by weight, even more preferably less than 0.01% by weight, most preferably such monomers (B3) and additional monomers are substantially absent, and most preferably even no other monomers other than monomers (B1) and (B2) are present at all.

[0354] The amount of the vinyl ester monomer (B1) is generally not less than 10% by weight (relative to the sum of (B1) and (B2)).

[0355] In an alternatively particularly preferred embodiment, based on the total weight of the graft polymer, the amounts of the monomers used are as follows:

[0356] (A) is 40% to 90%, preferably 50%, more preferably 80% of the polymer backbone as defined previously herein, preferably at least one of (A1), (A2) and (A3), as the grafting matrix;

[0357] (B) is 10% to 60%, preferably up to 50% and preferably 20%;

[0358] (B1) (vinyl ester) is the total amount of (B) minus the total amount of (B3);

[0359] (B2) is 0%;

[0360] (B3) (additional monomer) is 0% to 2%, preferably at most 1%, more preferably 0%, but in all cases at most 10% of the amount of (B1) and does not exceed the amount of (B2);

[0361] The amount of vinyl ester monomer (B1) is generally not less than 10% by weight (relative to the sum of (B1) and (B2));

[0362] Optional additional monomer (B3) and additional monomer other than (B1), (B2) and (B3) are preferably present only as impurities and not intentionally added for polymerization. More preferably, the amount is less than 1% by weight, more preferably less than 0.5% by weight, even more preferably less than 0.01% by weight based on the total weight of monomer (B1), and most preferably such monomer (B3) and additional monomer are substantially absent, and most preferably even completely absent any other monomer other than monomer (B1).

[0363] In each case based on the polymer side chain (B), the amount of (radical-forming) initiator (C) is preferably 0.1% to 5% by weight, especially 0.3% to 3.5% by weight.

[0364] 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 the graft monomers (B) and especially (B1), more preferably (B1) and (B2), even more preferably (B1), (B2) and (B3) are present only constantly at a low concentration (e.g. in total not exceeding 5% by weight) in the reaction mixture. This allows the reaction to be controlled and the graft polymer can be prepared in a controlled manner with the desired low polydispersity.

[0365] However, in order to ensure safe temperature control - especially when the polymerization starts at a high solid concentration and / or in large amounts and / or starts with a large amount of monomers present from the beginning - it is desirable and thus preferred to use additional and effective measures to control the temperature. This can be done by external and / or internal cooling; such cooling can be done by internal or external coolers (such as heat exchangers), or by using a reflux condenser when the solvent is at its boiling temperature or the solvent mixture is working at a given temperature / pressure combination.

[0366] The same measures can of course be used for the previously mentioned preferred embodiments, where the monomers are added over an extended period of time and thus the monomer concentration in the reaction volume remains low over time.

[0367] However, under such conditions, temperature control is usually not a key point, since the temperature is also at least partly controlled by the progress of the polymerization reaction by controlling the free radical concentration and the available amount of polymerizable monomers. Of course, this depends on the scale of the polymerization reaction. When the scale becomes large enough such that the ratio of the volume of the polymerization mixture to the surface becomes very large, such additional cooling as described above may be necessary for both variants - batch reaction or bulk reaction, which have a large amount of monomers present from the start, or semi - continuous or continuous polymerization reactions with typically a constant low monomer concentration.

[0368] However, this is well - known to the person skilled in the art of commercial - scale polymerization and can thus be adapted to these requirements.

[0369] According to the invention, the initiator (C) and the graft monomers (B) and in particular (B1) and / or (B2) and / or (B3) (preferably with "and" twice) are advantageously added in such a way that a low and substantially constant concentration of the undecomposed initiator and graft monomers (B) and in particular a constant but low amount of (B1) and in particular even more of (B2) (especially in the case when vinylpyrrolidone is selected as (B2)) is present in the reaction mixture. Based on the total amount of initiator metered during monomer addition, the proportion of the undecomposed initiator in the entire reaction mixture is preferably ≤ 15% by weight, especially ≤ 10% by weight.

[0370] In a more preferred embodiment, the method comprises at least one vinyl ester monomer (B1) and optionally at least one nitrogen-containing monomer (B2), optionally at least one other monomer (B3) and optionally at least one additional monomer, more preferably only monomers (B1) and (B2) in the presence of at least one polymer backbone (A) as defined herein, preferably selected from (A1), (A2) and (A3), a radical-forming initiator (C) and (if desired) up to 50% by weight, based on the sum of components (A), (B) and (C), of at least one organic solvent (D) at an average polymerization temperature at which the initiator (C) has a decomposition half-life of 40 to 500 min, in such a way that the fractions of unreacted graft monomers (B) and initiator (C) in the reaction mixture remain continuously substoichiometric with respect to the polymer backbone (A), where preferably at least 10 weight percent of the total amount of vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and where the remaining amount of vinyl ester can be any other known vinyl ester, where preferably at least 60, more preferably at least 70, even more preferably at least 80, even more preferably at least 90 weight percent, and most preferably substantially only (i.e., about 100 wt.% or even 100 wt.%) vinyl acetate is used as the vinyl ester (weight percent based on the total weight of the vinyl ester monomer B1 employed).

[0371] In an even more preferred embodiment of the foregoing previous embodiment, in addition to monomer (B1), monomer (B2) is substantially not employed, preferably (B1) comprises vinyl acetate, more preferably substantially only comprises vinyl acetate, all within the ranges and preferences given in the section on "Graft polymers of the invention".

[0372] In an alternative embodiment of the previous embodiment, in addition to monomer (B1), substantially only monomer (B2) is employed, preferably (B1) comprises vinyl acetate, more preferably substantially only comprises vinyl acetate, and preferably (B2) comprises a vinyl lactam, more preferably comprises vinyl pyrrolidone and even more preferably substantially comprises vinyl pyrrolidone, all within the ranges and preferences given in the section on "Graft polymers of the invention".

[0373] The average polymerization temperature for the main polymerization and the post-polymerization is suitably in the range of 50 °C to 140 °C, preferably 60 °C to 120 °C and more preferably 65 °C to 110 °C. Typically, the temperature for the post-polymerization is 5 °C to 40 °C higher than that for the polymerization.

[0374] The term "average polymerization temperature" is hereby intended to mean that, although the process is essentially isothermal, due to the exothermicity of the reaction, there may be temperature variations which are preferably kept within the range of + / - 10 °C, more preferably within the range of + / - 5 °C.

[0375] According to the invention, the initiator (C) (radical-forming) should have a decomposition half-life of from 40 to 500 min, preferably from 50 to 400 min and more preferably from 60 to 300 min at the average polymerization temperature.

[0376] Examples of suitable initiators (C) having a decomposition half-life of from 20 to 500 min in the temperature range from 50 °C to 140 °C are:

[0377] - tert-C4-C 12 - alkyl hydroperoxides and tert-(C9-C 12 - arylalkyl) hydroperoxides O-C2-C 12 - acylated derivatives such as tert-butyl peroxyacetate, 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 peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, tert-amyl peroxypivalate, tert-amyl peroxypivalate, tert-amyl peroxyneodecanoate, cumyl peroxyneodecanoate, tert-butyl peroxybenzoate, tert-amyl peroxybenzoate and di-tert-butyl diperoxyphthalate;

[0378] - tert-C8-C 14 - alkylene bisperoxides di-O-C4-C 12 - acylated derivatives such as 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane and 1,3-bis(2-neodecanoylperoxyisopropyl)benzene;

[0379] - di(C2-C 12 - alkanoyl) and dibenzoyl peroxides such as diacetyl peroxide, dipropionyl peroxide, disuccinyl peroxide, dioctanoyl 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;

[0380] - tert-C4-C5-alkyl peroxy(C4-C 12 - alkyl) carbonate such as tert-amyl peroxy(2-ethylhexyl) carbonate;

[0381] - di(C2-C12 -alkyl) esters such as di(n-butyl) peroxydicarbonate and di(2-ethylhexyl) peroxydicarbonate.

[0382] Depending on the average polymerization temperature, examples of particularly suitable initiators (C) are:

[0383] - At an average polymerization temperature of 50 °C to 60 °C:

[0384] tert-butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxyneopentanoate, tert-amyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneodecanoate, 1,3-bis(2-neodecanoylperoxyisopropyl)benzene, di(n-butyl) peroxydicarbonate and di(2-ethylhexyl) peroxydicarbonate;

[0385] - At an average polymerization temperature of 60 °C to 70 °C:

[0386] tert-butyl peroxyneopentanoate, tert-butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxyneopentanoate and bis(2,4-dichlorobenzoyl) peroxide;

[0387] - At an average polymerization temperature of 70 °C to 80 °C:

[0388] tert-butyl peroxyneopentanoate, tert-butyl peroxyneoheptanoate, tert-amyl peroxyneopentanoate, dipropionyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, bis(2,4-dichlorobenzoyl) peroxide and 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane;

[0389] - At an average polymerization temperature of 80 °C to 90 °C:

[0390] tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, dipropionyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, bis(3,5,5-trimethylhexanoyl) peroxide, benzoyl peroxide and bis(4-methylbenzoyl) peroxide;

[0391] - At an average polymerization temperature of 90 °C to 100 °C:

[0392] tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl monoperoxymaleate, tert-amyl peroxy-2-ethylhexanoate, benzoyl peroxide and bis(4-methylbenzoyl) peroxide;

[0393] - At an average polymerization temperature of 100 °C to 110 °C:

[0394] tert-butyl monoperoxymaleate, tert-butyl peroxyisobutyrate and tert-amyl peroxy(2-ethylhexyl) carbonate;

[0395] - At an average polymerization temperature of from 110 °C to 120 °C:

[0396] tert-butyl monoperoxymaleate, tert-butyl peroxy-3,5,5-trimethylhexanoate and tert-amyl peroxy(2-ethylhexyl) carbonate.

[0397] The preferred initiator (C) is an O-C4-C of a tert-C4-C5-alkyl hydroperoxide 12 - acyl derivative, and particularly preferred are tert-butyl peroxyneodecanoate and tert-butyl peroxy-2-ethylhexanoate.

[0398] Particularly advantageous polymerization conditions can be established effortlessly by precisely adjusting the initiator (C) and the polymerization temperature. For example, in the case of using tert-butyl peroxyneodecanoate, the preferred average polymerization temperature is from 60 °C to 80 °C, and in the case of using tert-butyl peroxy-2-ethylhexanoate, it is from 80 °C to 100 °C.

[0399] The polymerization reaction of the present invention can be carried out in the presence of (preferably a small amount of) solvent (D). Of course, a mixture of different solvents (D) can also be used. It is preferred to use a water-soluble or water-miscible organic solvent. However, water as the sole solvent is also possible in principle, but not preferred.

[0400] When using solvent (D) as a diluent, in each case based on the sum of components (A), (B1), optionally (B2), optionally (B3) and optional additional monomers and (C), it is usually used in an amount of from 1% to 40% by weight, preferably from 1% to 35% by weight, more preferably from 1.5% to 30% by weight, and most preferably from 2% to 25% by weight.

[0401] Examples of suitable solvents (D) include:

[0402] - 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;

[0403] - Polyhydric alcohols, preferably C2-C 10 - diols, more preferably C2-C6-diols, most preferably C2-C4-alkylene diols, such as ethylene glycol, 1,2-propanediol and 1,3-propanediol;

[0404] - Alkylene glycol ethers, preferably alkylene glycol mono(C1-C 12-alkyl) ethers and alkylene glycol di(C1-C6-alkyl) ethers, more preferably alkylene glycol mono- and di(C1-C2-alkyl) ethers, most preferably alkylene glycol mono(C1-C2-alkyl) ethers, such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, and propylene glycol monomethyl ether and propylene glycol monoethyl ether;

[0405] -polyalkylene glycols, preferably poly(C2-C4-alkylene) glycols having 2-20 C2-C4-alkylene glycol units, more preferably polyethylene glycols having 2-20 ethylene glycol units and polypropylene glycols having 2-10 propylene glycol units, most preferably polyethylene glycols having 2-15 ethylene glycol units and polypropylene glycols having 2-4 propylene glycol units, such as diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol;

[0406] -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) ethers;

[0407] -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;

[0408] -aliphatic ketones preferably having 3 to 10 carbon atoms, such as acetone, methyl ethyl ketone, diethyl ketone and cyclohexanone;

[0409] -cyclic ethers, especially tetrahydrofuran.

[0410] The solvent (D) is advantageously those solvents which are also used for formulating the graft polymers of the invention for use (for example in washing and cleaning compositions) and can thus remain in the polymerization product.

[0411] Preferred examples of these solvents are polyethylene glycols having 2-15 ethylene glycol units, polypropylene glycols having 2-6 propylene glycol units and especially the alkoxylation products of C6-C8-alcohols (alkylene glycol monoalkyl ethers and polyalkylene glycol monoalkyl ethers).

[0412] Particular preference is given here to considering C8-C 16-Alkoxylation products of alcohols, which allow the formulation of polymer mixtures that are free-flowing at 40 °C - 70 °C and have a very low polymer content at relatively low viscosities. Branches can 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 - 15 mol of ethylene oxide, C 13 / C 15 oxo alcohols or C 12 / C 14 or C 16 / C 18 fatty alcohols, and preferably considered is 2-propylheptanol alkoxylated with 1 - 15 mol of ethylene oxide and 1 - 3 mol of propylene oxide.

[0413] In an alternative embodiment, polymerization is carried out using a mixture of at least one organic solvent and water.

[0414] In a preferred embodiment, the amount of water during polymerization is low, preferably at most 10 wt.%, more preferably at most 5 wt%, and even more preferably at most 1% based on the total solvent.

[0415] In a further alternative embodiment, water is used as (D) for polymerization. However, water as the sole solvent is not preferred.

[0416] The radical initiator (C) is preferably used in the form of a concentrated solution in one of the aforementioned solvents. Of course, the concentration depends on the solubility of the radical initiator. Preferably, the concentration is as high as possible to allow the introduction of as little organic solvent as possible into the polymerization reaction. In the case where the initiator is soluble in water and thus water is used as the solvent for introducing the initiator, the concentration is not important from the perspective of the residual water amount.

[0417] Preferably, the amount of water during polymerization is at most 10 wt.%, preferably at most 5 wt.%, and more preferably at most 1 wt.% based on the total weight of the graft polymer (at the end of polymerization) or based on the total weight of (A) and (B) (at the start of polymerization).

[0418] In the process according to the invention, the polymer backbone (A), the graft monomer (B), the initiator (C) and, if appropriate, the solvent (D) are usually heated in a reactor to the selected average polymerization temperature.

[0419] According to the invention, the polymerization is carried out in such a way that an excess of polymer (polymer backbone (A) and the graft polymers formed) is continuously present in the reactor. The quantitative ratio of polymer to ungrafted monomer and initiator is generally ≥10:1, preferably ≥15:1 and more preferably ≥20:1.

[0420] The polymerization process according to the invention can in principle be carried out in various reactor types. Such reactor types are generally known and include any stirred reactor type, such as vessels, but also tubular reactors, reactor cascades from vessels or various tubes, etc.

[0421] The reactor used is preferably a stirred tank, in which initially the polymer backbone (A) (if appropriate) is completely or partially charged together with a specific total amount of the graft monomer (B), initiator (C) and solvent (D) generally up to 15% by weight and heated to the polymerization temperature, and the remaining amounts of (B), (C) and (if appropriate) (D) are metered in, preferably metered in separately. The remaining amounts of (B), (C) and (if appropriate) (D) are preferably metered in over a period of ≥2 h, more preferably ≥4 h and most preferably ≥5 h.

[0422] In the case of a particularly preferred, substantially solvent-free process variant, initially the entire amount of the polymer backbone (A) is charged as a melt, and the graft monomers (B1) and (if appropriate) (B2) and / or (B3) and also preferably the initiator (C) present in the form of a 10% to 50% by weight solution in one of these solvents (D) are metered in, controlling the temperature such that the selected polymerization temperature is maintained on average within a range of especially + / -10 °C, particularly + / -5 °C during the polymerization.

[0423] 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 also possible to start by metering in the solvent only at a later time by advanced polymerization or to add it batchwise.

[0424] The polymerization can be carried out at standard pressure or under reduced or elevated pressure. When the boiling point of the monomers (B1) and / or (B2) (and if used also monomer (B3)) and / or any solvent (D) used is exceeded at the selected pressure, the polymerization is carried out with reflux cooling.

[0425] A post-polymerization method step can be added after the main polymerization reaction. To this end, an additional amount of initiator (dissolved in a solvent) can be added over a period of 0.5 hours and typically up to 3 hours, preferably about 1 to 2 hours, more preferably about 1 hour (however, such a duration also depends on the scale of the reactor), wherein the free radical initiator and the solvent for the initiator are typically - and preferably - the same as the initiator and solvent used for the main polymerization reaction. Of course, different free radical initiators and / or different solvents can also be used.

[0426] The temperature of the post-polymerization method step can be the same as or can be increased compared to the temperature in the main polymerization reaction (which is preferred in the present invention). In the case of an increase, it can typically be about 5 °C to 40 °C higher, preferably 10 °C to 20 °C.

[0427] A certain period of time can be waited between the post-polymerization and the main polymerization, during which the main polymerization reaction continues, and then the post-polymerization reaction is started by beginning to add additional free radical initiator.

[0428] For solvents having a boiling point of approximately less than 110 °C - 120 °C at atmospheric pressure, such solvents can - as a purification step - be partially or substantially completely removed by thermal distillation or vacuum distillation either entirely at ambient pressure or reduced pressure or by stripping with a gas such as steam or nitrogen (such as stripping with steam made from water), preferably vacuum distillation, while higher boiling solvents will generally remain in the obtained polymer product.

[0429] When mercaptoethanol is used as a chain transfer regulator, steam distillation is the preferred purification step. Thus, higher boiling solvents such as 1-methoxy-2-propanol, 1,2-propanediol, and tripropylene glycol will remain in the polymer product, and therefore when such solvents are only used for introducing the initiator, their amount should be minimized as much as possible by using the highest possible concentration of free radical initiator, unless such solvents also form part of the formulation in which the graft polymer will be used.

[0430] The graft polymers of the present invention prepared by the method as defined herein may contain a certain amount of ungrafted polymer made from vinyl esters ("ungrafted side chains"), for example, in the case of using only vinyl acetate, polyvinyl acetate, and / or - when other monomers are used - homopolymers and copolymers of vinyl esters and other monomers. Depending on the reaction conditions, the amount of such ungrafted vinyl ester - homopolymers and copolymers may be high or low, but is preferably reduced and thus low. By this reduction, the amount of graft side chains is preferably increased. Such reduction can be achieved by suitable reaction conditions, such as the dosage and relative amounts of vinyl esters and free radical initiators, and is also related to the amount of the main chain present. Such reaction control and the necessary method steps are generally known to those skilled in the art, and specific guidance is given herein.

[0431] This adjustment of the grafting degree and the amount of ungrafted polymer can be used to optimize the properties in a particular area of interest, such as certain (e.g., detergent -) formulations, application areas, or desired properties such as cleaning.

[0432] It is believed that the conditions considered favorable herein promote - presumably - a higher grafting degree; such a higher grafting degree is associated with better properties. However, this presumably higher grafting degree does not impair biodegradation - which is attributed to the ester bonds in the main chain, which can "compensate" for the lower biodegradation of the graft polymer with a higher grafting degree - as seen in "conventional graft polymers" based on polyalkylene oxides as the main chain.

[0433] The disadvantage is that it is extremely difficult, if not impossible, to actually verify such a grafting degree on the polymer, especially as the molecular weight of the polymer increases, because the total amount of grafting sites in the polymer is usually very low compared to the molecular weight; thus, given the current analytical tools, the signal - to - noise ratio is unfavorable for the polymer.

[0434] In another - alternative - embodiment of the present invention, after the polymerization reaction and thus after obtaining such a graft polymer, the polymer side chains (B) of the graft polymer according to the present invention are completely or partially hydrolyzed, preferably partially hydrolyzed, more preferably up to 50 mol%, and preferably 20 mol%, more preferably 20 mol% to 50 mol%, even more preferably 30 mol% to 45 mol%, such as about 40 mol% hydrolysis, based on the total molar amount of (B1) used. This means that the complete or at least partial hydrolysis of the polymer side chains (B) of the graft polymer is carried out in an additional method step after the completion of the polymerization process of the polymer side chains (B) (including after an optional post - polymerization step, if used).

[0435] In another alternative embodiment, no hydrolysis is carried out on the graft polymer after the completion of the polymerization process of the polymer side chains (B).

[0436] Due to this complete or at least partial hydrolysis of the polymer side chain (B) of the graft polymer according to the invention, the corresponding side chain units derived from at least one vinyl ester monomer (B1) are converted from the corresponding ester functional groups to alcohol functional groups in the polymer side chain (B). It must be noted that due to the stability aspects of "vinyl alcohol"-monomers, the corresponding vinyl alcohol is not suitable for use as a monomer during the polymerization of the polymer side chain (B). In order to obtain alcohol functional groups (hydroxyl substituents) in the polymer side chain (B) of the graft polymer according to the invention, the alcohol functional groups are typically introduced by hydrolyzing the ester functional groups of the side chains.

[0437] From a theoretical point of view, each ester functional group of the polymer side chain (B) can be partially or completely replaced by an alcohol functional group (hydroxyl group). In this case, the polymer side chain is completely hydrolyzed ("saponified").

[0438] The hydrolysis can be carried out by any method known to those skilled in the art. For example, the hydrolysis can be induced by adding a suitable base, such as sodium hydroxide or potassium hydroxide. Such hydrolysis methods are known from the prior art.

[0439] In a preferred embodiment of the previous example, vinyl acetate is used as monomer (B1) and vinyl pyrrolidone is used as monomer (B2) and no other monomers are used in addition to (B1) and (B2), and the polymer part derived from vinyl acetate is partially hydrolyzed after polymerization, preferably in an amount of 20 mol% to 50 mol%, more preferably 30 mol% to 45 mol%, such as - most preferably - about 40 mol% based on the total moles of (B1) used.

[0440] The graft polymer according to the invention, i.e. the polymer solution obtained from the process, can also be subjected to means for concentration and / or drying.

[0441] The obtained graft polymer solution can be concentrated to increase the solid polymer concentration by subjecting the polymer solution to means for removing part of the volatiles and especially the solvent. This can be achieved by a distillation process (such as thermal or vacuum distillation), or by stripping with a gas (such as steam or an inert gas such as nitrogen or argon), and carried out until the desired solid content is obtained. Such a process can be combined with the purification step as disclosed previously, in which the obtained graft polymer solution is purified by removing part or all of the volatile components such as volatile solvents and / or unreacted volatile monomers, by removing the desired amount of solvent.

[0442] The graft polymer solution can also be further concentrated or dried after the main polymerization and / or optional post-polymerization steps and optional purification steps by subjecting the graft polymer solution to means for partially or completely removing volatiles, such as - for concentration - distillation processes such as thermal or vacuum distillation, or stripping with a gas such as steam or an inert gas such as nitrogen or argon until the desired solids content is obtained, and / or drying such as roller-drum drying, spray-drying, vacuum drying or freeze-drying, preferably - mainly for cost reasons - spray-drying. Such drying processes can also be combined with agglomeration or granulation processes, such as spray-agglomeration, granulation or drying in a fluidized bed dryer.

[0443] Accordingly, the process of the present invention preferably encompasses at least one additional process step selected from i) to iv), where i) post-polymerization; ii) purification; iii) concentration; and iv) drying.

[0444] More preferably, the process as detailed in any of the embodiments defined herein includes at least one additional process step selected from:

[0445] i) A post-polymerization process step that occurs after the main polymerization reaction, where an additional amount of initiator (optionally dissolved in the solvent) is preferably added over a period of 0.5 hour and up to 3 hours, preferably about 1 to 2 hours, more preferably about 1 hour, and the free radical initiator and the solvent for the initiator are typically - and preferably - the same as those used for the main polymerization reaction; and where after the polymerization reaction and before the post-polymerization reaction, preferably a period of time is waited during which the main polymerization reaction continues, and then the post-polymerization reaction is started by beginning to add additional free radical initiator, such a period of time is preferably 10 minutes and up to 4 hours, preferably up to 2 hours, even more preferably up to 1 hour, and most preferably up to 30 minutes; and where the temperature of the post-polymerization process step is preferably the same as in the main polymerization reaction, or increased, compared to the temperature of the main polymerization reaction, such an increase being preferably about 5 °C to 40 °C, preferably 10 °C to 20 °C;

[0446] ii) A step of subjecting the graft polymer obtained from the main polymerization or - if carried out - the post-polymerization process step to means for purification, concentration and / or drying to remove some or almost all of the remaining solvent (as long as they are removable due to their boiling points) and / or volatiles such as residual monomers, where

[0447] a. The concentration is carried out by, preferably applying a distillation process such as thermal or vacuum distillation, preferably vacuum distillation, and / or applying stripping with a gas such as steam or an inert gas such as nitrogen, preferably using steam from water, to remove a portion of the solvent and optionally also volatiles - whereby this step additionally serves as a means for purification - to increase the solid polymer concentration - and optionally also for purification, carrying it out until the desired solid content and optionally also purity are obtained, preferably carrying it out until the desired portion or all of the volatile components such as volatile solvents and / or unreacted volatile monomers are removed;

[0448] b. The drying is carried out by subjecting the graft polymer containing at least a residual amount of volatiles such as remaining solvent and / or unreacted monomers, etc. to means for removing the volatiles, such as drying using rollers, spray dryers, vacuum drying or freeze drying, preferably - mainly for cost reasons - spray drying; and optionally combining such a drying method step with means for agglomeration or granulation to obtain agglomerated or granulated graft polymer particles, such a process preferably being selected from spray - agglomeration, granulation or drying in a fluidized bed dryer, spray - granulation device, etc.

[0449] Definition

[0450] In principle, the graft polymers of the present invention can be used in any application to replace conventional graft polymers of the same or very similar composition (in terms of the relative amounts of the polymer backbone and graft monomers, especially when the type and amount of graft monomers are similar or equivalent). Such applications are, for example:

[0451] All compared to the corresponding polymers or graft polymers according to the prior art, redeposition of dirt and removal of stains, avoidance or reduction of redeposition or ashing or deposition of solids, dispersions of active substances in formulations of agrochemicals, pigments, dyes, inorganic salts, etc., inhibition of crystal growth, including for inhibiting the formation of gas hydrates and / or reducing sedimentation and / or agglomeration, improving the stability of pigment dispersions, hydrophobization of surfaces, reduction of microbial growth on surfaces, and / or odor control, etc.

[0452] Typical applications are:

[0453] Technical applications: Such compositions and formulations include gums for any kind of non - aqueous and - preferably - water - based liquid formulations or solid formulations, and are used as dispersants in any kind of dispersions, such as in oilfield applications, automotive applications, typically applications where solids or liquids are to be dispersed in another liquid or solid.

[0454] Lacquers, paints and colorant formulations: Such compositions and formulations include non-aqueous and - preferably - water-based lacquers and colorants, paints, finishes.

[0455] Agricultural formulations: Such compositions and formulations include formulations and compositions containing agrochemical active substances in liquid, semi-solid, mixed liquid-solid or solid environments.

[0456] Aroma chemical formulations: Such compositions and formulations include formulations that dissolve or disperse aroma chemicals in liquid or solid compositions to uniformly disperse and / or maintain their stability so as to maintain their aromatic properties over an extended period of time; also covered are compositions that exhibit the release of aroma chemicals over time, such as delayed-release or sustained-release formulations.

[0457] The graft polymers of the present invention obtainable or obtained by the methods as defined herein can improve the overall biodegradation ratio of such formulations, compositions and products by replacing non-biodegradable polymers of similar structure or properties. Thus, they can be advantageously used - depending in part on monomer B used for grafting and thus adjusting their properties according to the specific needs of a particular application; such monomer substitution patterns may also be derived from the prior art of similar graft polymers based on simple PEG and polyalkylene glycols.

[0458] Specifically, and beyond the performance in a certain type of application, compared with previously known graft polymers, when used in such compositions or products, the graft polymers according to the present invention result in improved biodegradability.

[0459] Therefore, another subject of the present invention is the use of the graft polymers of the present invention and / or obtainable or obtained by the methods of the present invention and / or as detailed above in cleaning compositions, fabric and home care products, particularly in cleaning compositions for improved removal of oily and fatty stains, removal of solid dirt such as clay, prevention of graying of fabric surfaces, and / or as scale inhibitors, wherein the cleaning composition is preferably a laundry detergent formulation and / or a dishwashing detergent formulation, more preferably a liquid laundry detergent formulation and / or a liquid manual dishwashing detergent formulation.

[0460] Accordingly, 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 previously in any of the foregoing applications of this chapter: such as fabric care and household care products, in cosmetic and personal care formulations, as crude oil demulsifiers, in technical applications (including in pigment dispersions for inkjet inks), in formulations for electroplating, in cementitious compositions, in agrochemical formulations as, for example, dispersants, crystal growth inhibitors and / or solubilizers, in paint and colorant formulations, for textile and leather treatment products used during or after production, formulations containing inorganic salts such as especially silver salts, mining, metal production and treatment (including metal refining and metal quenching), purification of liquids such as industrial, production or consumer wastewaters, preferably in agrochemical and cleaning compositions and in fabric and household care products, especially in cleaning compositions for improved removal of oily and fatty stains, removal of solid dirt such as clay, prevention of greying of the fabric surface, and / or antiscaling agents, and most preferably - for inhibiting the transfer of dyes, wherein the cleaning composition is preferably a laundry detergent formulation, more preferably a liquid laundry detergent formulation.

[0461] Accordingly, another subject of the present invention is also a cleaning composition, a fabric care and household care product, an industrial and institutional cleaning product, an agrochemical formulation, or a formulation or product for any of the previously mentioned applications and application areas, preferably in laundry detergents, in cleaning compositions and / or in fabric and household care products, each containing at least one graft polymer as defined above or obtained or obtainable by the process of the present invention and / or as detailed herein.

[0462] Accordingly, a preferred subject of the present invention is also the use of at least one graft polymer of the present invention and / or at least one graft polymer obtained or obtainable by the process of the present invention in fabric care and household care products, industrial and institutional cleaning products, agrochemical formulations, or a formulation or product for any of the previously mentioned applications and application areas, preferably in cleaning compositions and in fabric treatment agents, fabric care products and fabric washing products, more preferably in laundry detergent formulations, even more preferably in liquid laundry detergent formulations. In particular, the graft polymers of the present invention are used in such compositions / products / formulations for improved inhibition of dye transfer.

[0463] Uses of the present invention and compositions / products of the present invention cover uses of graft polymers as detailed herein and / or as obtainable or obtained by the methods of the present invention, such graft polymers being similar to the graft polymers having the polymer structures described in any of its embodiments (including any variants mentioned, and more specifically any preferred, more preferred, etc. embodiments) disclosed hereinbefore as detailed above.

[0464] Laundry detergents, cleaning compositions and / or fabric and home care products are known per se to those skilled in the art. Any compositions, etc. related to the corresponding uses known to those skilled in the art can be used in the context of the present invention.

[0465] In a preferred embodiment, it is a cleaning composition and / or fabric and home care product and / or industrial and institutional cleaning product, which comprises at least one graft polymer as defined above. In particular, it is a cleaning composition for improved cleaning performance and / or - preferably "and" - improved anti-redeposition (e.g., in terms of soil redeposition and stain removal), preferably a laundry detergent formulation and / or a hand dishwashing detergent formulation, more preferably a liquid laundry detergent formulation and / or a liquid hand dishwashing detergent formulation.

[0466] The graft polymer supports the removal of various hydrophobic and hydrophilic soils from textiles or hard surfaces by surfactants, such as body soils, food and grease soils, particulate soils such as clay or carbon black, grass soils, make-up, engine oil, etc., and thus improves the washing and cleaning performance of the formulation.

[0467] Furthermore, the graft polymer also better disperses the removed soils in the wash liquor or cleaning liquor and prevents their redeposition onto the surface of the washed or cleaned material. Herein, the removed soils include all typical soils present during the laundry process, such as body soils, food and grease soils, particulate soils such as clay or carbon black, grass soils, make-up, engine oil, etc. Such anti-redeposition effects can be observed on various fabric types, including cotton, polycotton, polyester, copolymers of polyether / polyurea (Spandex TM ) etc. Additionally, such anti-redeposition effects are also effective for fabrics having a history of fabric softeners, or when fabric washing is carried out in the presence of fabric softeners or other laundry additives such as freshness beads or bleach.

[0468] In one embodiment, it is further preferred in the present invention that the cleaning composition additionally comprises (in addition to at least one graft polymer as described above) at least one enzyme, which is preferably selected from one or more enzymes, which may optionally further comprise at least one enzyme, which is preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, deoxyribonucleases, xylanases, oxidoreductases, dispersin, mannanases and peroxidases (oxicoreductase), and combinations of at least two of the foregoing types, preferably at least one enzyme is selected from lipases.

[0469] Accordingly, another subject of the present invention is a cleaning composition comprising at least one graft polymer as defined above, such as fabric and home care products and industrial and institutional (I&I) cleaning products, and in particular a cleaning composition for improved primary cleaning, improved whiteness, or both, preferably both (such effects as detailed previously).

[0470] At least one graft polymer as described herein is present in the cleaning composition of the present invention in an amount ranging from about 0.01% to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1% to about 10%, and most preferably from about 0.5% to about 5% relative to the total weight of such composition or product; such cleaning composition may - and preferably does - further comprise a surfactant system in an amount of about 1% to about 70% by weight.

[0471] Preferably, such a cleaning composition of the present invention is a fabric and home care product or an industrial and institutional (I&I) cleaning product, preferably a fabric and home care product, more preferably a laundry detergent or a hand dishwashing detergent, which comprises at least one graft polymer of the present invention, and optionally further comprises at least one surfactant or surfactant system, providing improved removal, dispersion and / or emulsification of dirt and / or modification of the treated surface and / or maintenance of whiteness of the treated surface.

[0472] Even more preferably, the cleaning composition of the present invention comprising at least one graft polymer of the present invention and optionally further comprising at least one surfactant or surfactant system - as detailed previously - is for cleaning and anti-redeposition performance in laundry and dishwashing applications, even more specifically for improved cleaning and anti-redeposition performance (such effects as detailed previously) (such as those on fabrics and dishes), and may additionally comprise at least one enzyme selected from the list consisting of: optionally further comprising at least one enzyme, which is preferably selected from one or more of optionally further comprising at least one enzyme, which is preferably selected from one or more of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, deoxyribonucleases, xylanases, oxidoreductases, dispersing enzymes, mannanases and peroxidases, and combinations of at least two of the foregoing types, preferably selected from one or more of lipases, hydrolases, amylases, proteases, cellulases, and combinations of at least two of the foregoing types, more preferably at least one enzyme is selected from lipases.

[0473] In one embodiment of the present invention, the graft polymer of the present invention can be used for improved cleaning and anti-redeposition performance (such effects as detailed previously) such as primary washing and / or removal of particulate stains and / or oily and fatty stains, and / or additionally for whiteness maintenance, preferably in laundry care. In another preferred embodiment, the graft polymer of the present invention can be used for reducing the graying of fabrics (anti-graying), preferably more than one of the previously mentioned effects is present, i.e., more than one of improved cleaning, anti-redeposition, primary washing, removal of particulate stains and / or oily and fatty stains, whiteness maintenance and / or anti-graying is exhibited by the graft polymer of the present invention.

[0474] In another embodiment, the graft polymer of the present invention can be used for improved dye transfer inhibition, i.e., preventing dyes from transferring from one fabric to another, either by direct contact or via the wash liquor. For such applications, it is preferred that the graft polymer contains at least one monomer (B2) as defined herein for such cases. More preferably, (B2) is at least one vinyl lactam, even more preferably at least one vinyl pyrrolidone and / or caprolactam, most preferably vinyl pyrrolidone. Such graft polymers containing such (B2) are defined herein with suitable compositions and methods for obtaining such graft polymers.

[0475] In a preferred embodiment, the cleaning composition of the present invention is a liquid or solid laundry detergent composition.

[0476] In another preferred embodiment, the cleaning composition of the present invention is a liquid or solid (such as powder or tab / single-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.

[0477] In another embodiment, the cleaning composition of the present invention is a hard surface cleaning composition, which can be used to clean various surfaces, such as hardwood, tile, ceramic, plastic, leather, metal, glass.

[0478] In one embodiment, the graft polymer of the present invention can be used in a cleaning composition containing a surfactant system that includes C10-C15 alkylbenzene sulfonate (LAS) as the main surfactant and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

[0479] In further embodiments, the graft polymer of the present invention can be used in any type of cleaning composition, such as laundry detergents, etc., which contain C8-C18 linear or branched alkyl ether sulfates having 1-5 ethoxy units as the main surfactant and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

[0480] In further embodiments, the graft polymer of the present invention can be used in any type of cleaning composition, such as laundry detergents, etc., which contain C12-C18 alkyl ethoxylate surfactants having 5-10 ethoxy units as the main surfactant and one or more additional surfactants selected from anionic, cationic, amphoteric, zwitterionic or other nonionic surfactants, or mixtures thereof.

[0481] In one embodiment of the present invention, the graft polymer is a component of a cleaning composition such as preferably a laundry or dishwashing formulation, more preferably a liquid laundry or manual dishwashing formulation, each of which additionally contains at least one surfactant, preferably at least one anionic surfactant.

[0482] In such laundry detergents, cleaning compositions or fabric and home care products of the present invention as detailed in any embodiment of the present invention and specifically any previous most preferred embodiment, at least one graft polymer - when used solely as a dye transfer inhibitor and thus - preferably - contains (B2)-monomers in an amount greater than 5 wt.% based on the total monomers (B) - as detailed in any such embodiment disclosed herein (including specifically any previous most preferred embodiment in this chapter disclosing such graft polymers) - 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% and even more preferably from about 0.2% to about 4% and most preferably in an amount up to 2%, each based on the weight% of the total weight of such composition or product, all values between, and including all ranges obtained by selecting any lower limit and combining it with any upper limit, each based on the weight% of the total weight of such composition or product, and optionally further contains at least one enzyme, which is preferably selected from one or more lipases, selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, cutinases, deoxyribonucleases, xylanases, mannanases, dispersing enzymes, oxidoreductases, lactases and peroxidases and combinations of at least two of the foregoing types, and further optionally contains an antimicrobial agent selected from the group consisting of 2-phenoxyethanol; preferably contains the antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition, more preferably contains 0.1% to 2% of phenoxyethanol, and optionally further contains 4,4'-dichloro-2-hydroxy diphenyl ether at a concentration of from 0.001% to 3%, preferably from 0.002% to 1%, more preferably from 0.01% to 0.6% each by weight of the composition, and further contains a surfactant system in an amount of from about 1% to about 70% by weight of such detergent, composition or product.

[0483] In such laundry detergents, cleaning compositions or fabric and home care products of the present invention as detailed in any embodiment of the present invention and in particular any previous most preferred embodiment, at least one graft polymer - when not employed as a dye transfer inhibitor and thus - preferably - does not contain (B2)-monomers or contains (B2)-monomers in an amount of less than 10 wt.%, preferably less than 5 wt.%, based on the total monomers (B) - as detailed in any such embodiment disclosed herein (including in particular any previous most preferred embodiment in this chapter that discloses such graft 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% and even more preferably from about 0.2% to about 4%, and most preferably in an amount up to 2%, each based on the weight % of the total weight of such composition or product, all values therebetween, and including all ranges obtained by choosing any lower limit and combining it with any upper limit, each based on the weight % of the total weight of such composition or product, and optionally further comprises at least one enzyme, which is preferably selected from one or more lipases, selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, cutinases, deoxyribonucleases, xylanases, mannanases, dispersing enzymes, redox enzymes, lactases and peroxidases and combinations of at least two of the foregoing types, and further optionally comprises an antimicrobial agent selected from the group consisting of 2-phenoxyethanol; preferably comprises the antimicrobial agent in an amount in the range of 2 ppm to 5% by weight of the composition, more preferably comprises 0.1% to 2% of phenoxyethanol, and optionally further comprises 4,4'-dichlor-2-hydroxy diphenyl ether at a concentration of from 0.001% to 3%, preferably from 0.002% to 1%, more preferably from 0.01% to 0.6% by weight of the composition, and further comprises a surfactant system in an amount of from about 1% to about 70% by weight of such detergent, composition or product.

[0484] In a further embodiment, the present invention also encompasses a composition comprising a graft polymer as described previously herein, further comprising an antimicrobial agent (preferably selected from the group consisting of 2-phenoxyethanol) as disclosed hereinafter; more preferably comprises the antimicrobial agent in an amount in the range of 2 ppm to 5% by weight of the composition; even more preferably comprises 0.1% to 2% of phenoxyethanol.

[0485] In a further embodiment, the present invention also encompasses a method for preserving an aqueous composition against microbial contamination or growth, said composition comprising a graft polymer as previously described herein, said composition being preferably a detergent composition, said method comprising adding at least one antimicrobial agent selected from antimicrobial agents disclosed hereinafter, said antimicrobial agent being preferably 2-phenoxyethanol.

[0486] In a further embodiment, the present invention also encompasses a composition, preferably a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dish composition, even more preferably a liquid laundry detergent composition or a liquid fabric softener composition for use in laundering, said composition comprising a graft polymer as previously described herein, said composition further comprising 4,4'-dichlor-2-hydroxy-diphenyl ether at a concentration of from 0.001% to 3%, preferably from 0.002% to 1%, more preferably from 0.01% to 0.6% by weight of the composition, respectively.

[0487] In a further embodiment, the present invention also encompasses a method of laundering fabrics or cleaning hard surfaces, said method comprising treating the fabrics or hard surfaces with a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dish composition, even more preferably a liquid laundry detergent composition or a liquid fabric softener composition for use in laundering, said composition comprising a graft polymer as previously described herein, said composition further comprising 4,4'-dichlor-2-hydroxy-diphenyl ether.

[0488] The choice of additional surfactant in these embodiments can depend on the application and the desired benefits.

[0489] The graft polymers according to the invention can be used, for example, in cleaning compositions and / or fabric and home care products. They result in at least comparable and preferably even improved performance within such compositions or products, where the graft polymers of the invention can replace similar graft polymers which, however, are not biodegradable or exhibit much lower biodegradability.

[0490] Description of cleaning compositions, formulations and their ingredients

[0491] As used herein, when used in the claims or examples, the articles "a" and "an" shall be understood to mean one or more of what is claimed or described. As used herein, the terms "include" and "including" are meant to be non-limiting and thus cover more than the particular item(s) recited after these words.

[0492] As used herein, the term "about" encompasses the exact numerical value "X" being referred to, e.g., "about X %" etc., as well as small variations of X, including deviations from X - 5% to + 5% (for this calculation, X is set to 100 %), preferably - 2% to + 2%, more preferably - 1% to + 1%, even more preferably - 0.5% to + 0.5% and even smaller variations. Of course, if the given value X itself is already "100 %" (such as for purity etc.), then the term "about" can clearly and thus indeed only mean its deviation less than "100".

[0493] Similarly, the ranges and values disclosed herein should not be construed as being strictly limited to the exact numerical values recited. Instead, in addition to the exact numerical values, functionally equivalent ranges around that value are also encompassed. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

[0494] The term "water - free" means that the composition contains no more than 5 wt.-% water, based on the total amount of the solvent, in another embodiment no more than 1 wt.-% water, based on the total amount of the solvent, and in a further embodiment the solvent contains no water at all.

[0495] The compositions disclosed herein can "comprise" the components disclosed herein (i.e., contain other ingredients), "consist essentially of the components disclosed herein" (primarily or almost exclusively contain the ingredients mentioned and only very small amounts of other ingredients as impurities mainly), or "consist of the components disclosed herein" (i.e., contain only the ingredients mentioned and additionally may contain only impurities inevitable in the technical environment, preferably only these ingredients).

[0496] Similarly, the terms "substantially free of", "substantially free from" or "substantially not (containing / comprising)" can be used herein; this means that the indicated material is present in a very small amount not intentionally added to the composition to form part of it, or, preferably, is not present at an analytically detectable level. It means including compositions in which the indicated material is present only as an impurity in one of the other materials intentionally included. If any, the indicated material can be present at a level less than 1%, or even less than 0.1%, or even far less than 0.01%, or even 0% by weight of the composition.

[0497] Generally, as used herein, the term "obtainable by" means that the corresponding product does not necessarily have to be produced (i.e., obtained) by the corresponding method or process described in the corresponding specific context, but includes products that exhibit all the characteristics of products produced (obtained) by the corresponding method or process, where the product is not actually produced (obtained) by such method or process. However, the term "obtainable by" also includes the more restrictive term "obtained by", i.e., products actually produced (obtained) by the method or process described in the corresponding specific context.

[0498] Unless otherwise mentioned, all component or composition levels refer to the active part of the component or composition and do not include impurities that may be present in commercially available sources of such components or compositions, e.g., residual solvents or by-products.

[0499] Unless otherwise indicated, all temperatures herein are in degrees Celsius (°C). Unless otherwise specified, all measurements herein are made at 20 °C and at atmospheric pressure. In all examples of this disclosure, unless otherwise specifically stated, all percentages are by weight of the total composition. Unless otherwise specifically stated, all ratios are weight ratios.

[0500] Throughout this specification, the term "inventive compound" may be used in place of "inventive (graft) polymer(s)" and "(graft) polymer(s) of this (present) invention", meaning that these compounds are as disclosed herein in the present invention, defined by their structure and / or their production method or obtainable by the methods defined herein.

[0501] The definitions given in the "Definitions" section and their preferred options are included as part of the present invention as described herein.

[0502] The present invention encompasses the specific embodiments described throughout this disclosure as part of the present invention; various additional options are disclosed in the present invention specification as "optional", "preferred", "more preferred", "even more preferred" or "most preferred" (or "preferably", etc.), and the options of the specific embodiments can be selected individually and independently (unless such independent selection is impossible due to the nature of the feature or if such independent selection is explicitly excluded) and then combined with any other embodiment (wherein other such options and preferences can also be selected individually and independently, unless such independent selection is impossible due to the nature of the feature or if such independent selection is explicitly excluded), and each and any and all such possible combinations are included as separate embodiments as part of the present invention.

[0503] Cleaning compositions

[0504] As used herein, the phrase " Industrial and institutional cleaning " includes compositions and formulations designed for cleaning soiled materials. Such compositions and formulations include those designed for cleaning any kind of soiled material or surface.

[0505] Compositions for " Fabric care compositions " include such cleaning compositions designed for industrial and institutional cleaning, such as those for cleaning any kind of soiled material or surface, such as hard surface cleaners for any kind of surface (including tile, carpet, PVC surface, wooden surface, metal surface, painted surface).

[0506] The phrase " Compositions for fabric and home care " means including compositions and formulations designed for treating fabrics. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric brightening compositions, laundry pre-wash compositions, laundry pre-treatment agents, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, wash additives, post-rinse fabric treatment agents, ironing aids, unit dose formulations, delayed delivery formulations, detergents contained on or in porous substrates or non-woven sheets, and other suitable forms that would be apparent to those skilled in the art in view of the teachings herein and are detailed below when describing the compositions. Such compositions can be used as pre-wash treatment agents, post-wash treatment agents, or can be added during the rinse or wash cycle of a washing operation, and are further detailed below when describing the uses and applications of the graft polymers of the present invention and compositions containing such graft polymers.

[0507] " Cleaning additives”including cleaning compositions, which include but are not limited to laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric brightening compositions, laundry pre-wash agents, laundry pretreatment agents, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, wash additives, post-rinse fabric treatment agents, ironing aids, dishwashing compositions, hard surface cleaning compositions, unit dose formulations, delayed delivery formulations, detergents contained on or in porous substrates or nonwoven sheets, light-duty liquid detergent compositions, heavy-duty liquid detergent compositions, detergent gels commonly used for laundry, bleaching compositions, laundry additives, fabric enhancer compositions, and other suitable forms that would be apparent to those skilled in the art in view of the teachings herein. Such compositions can be used as pre-wash treatments, post-wash treatments, or can be added during the rinse or wash cycles of a washing operation, preferably during the wash cycle of a laundry or dishwashing operation. More preferably, such compositions for fabric and home care are laundry cleaning compositions, laundry care products, or laundry washing products, and most preferably liquid laundry detergent formulations or liquid laundry detergent products.

[0508] The cleaning compositions of the present invention can be in any form, i.e., in the form of a "liquid" composition, including composition types containing liquids such as pastes, gels, emulsions, foams, and mousses; in the form of solid compositions, such as powders, granules, microcapsules, beads, noodles, pearlescent balls, agglomerates, tablets, granule compositions, sheets, lozenges, beads, fibrous products, strips, flakes; or mixtures thereof; types delivered in single-, double-, or multi-compartment bags or containers; single-phase or multi-phase unit doses; spray or foam detergents; pre-moistened wipes (i.e., cleaning compositions combined with nonwoven materials, such as the cleaning compositions discussed in US 6,121,165, Mackey et al.); dry wipes (i.e., cleaning compositions combined with nonwoven materials, such as the cleaning compositions discussed in US 5,980,931, Fowler et al.), which are activated by the user or consumer with water; and other homogeneous, heterogeneous, single-phase or multi-phase cleaning product forms.

[0509] The composition can be encapsulated in a single or multi-compartment bag. The multi-compartment bag can have at least two, at least three, or at least four compartments. The multi-compartment bag can include side-by-side and / or stacked compartments. The composition contained in the bag or its compartments can be liquid, solid (such as powder), or a combination thereof.

[0510] Non-limiting examples of "liquid" / "liquid composition" include light-duty and heavy-duty liquid detergent compositions, fabric enhancers, detergent gels commonly used for laundry, bleaching and laundry additives. Gases, such as suspended air bubbles, or solids, such as particles, may be contained in the liquid.

[0511] The liquid cleaning composition of the present invention preferably has a viscosity of 50 to 10,000 mPa·s; at 20 1 / s and 20 °C, the liquid dishwashing composition for hand washing (also known as the liquid manual "dishwashing composition") has a viscosity preferably of 100 to 10,000 mPa·s, more preferably 200 to 5,000 mPa·s and most preferably 500 to 3,000 mPa·s; at 20 1 / s and 20 °C, the liquid laundry cleaning composition has a viscosity preferably of 50 to 3,000 mPa·s, more preferably 100 to 1,500 mPa·s and most preferably 200 to 1,000 mPa·s.

[0512] The liquid cleaning composition of the present invention can have any suitable pH value. Preferably, the pH of the composition is adjusted to between 4 and 14. More preferably, the composition has a pH of 6 to 13, even more preferably 6 to 10, and most preferably 7 to 9. The pH of the composition can be adjusted using pH-modifying ingredients known in the art and is measured at 25 °C in demineralized water at a 10% product concentration. For example, NaOH can be used and the actual weight % of NaOH can be varied and trimmed to the desired pH, such as pH 8.0. In one embodiment of the present invention, the pH > 7 is adjusted by using amines, preferably alkanolamines, more preferably triethanolamine.

[0513] Cleaning compositions, such as fabric and home care products and formulations for industrial and institutional cleaning, more specifically such as laundry detergents and dishwashing detergents for hand washing, are known to those skilled in the art. Any composition etc. known to those skilled in the art (in combination with their respective uses) can be used within the context of the present invention by including at least one polymer of the present invention, preferably at least one polymer in an amount suitable for exhibiting certain properties within such a composition (especially when such a composition is used in its field of use).

[0514] One aspect of the present invention is also the use of the polymer of the present invention as an additive for detergent formulations, especially for liquid detergent formulations, preferably concentrated liquid detergent formulations, or single-dose single-use additives for laundry.

[0515] All such cleaning compositions, their ingredients (including (auxiliary) cleaning additives), their general and more specific compositions are known, as shown for example in publications 800542 and 800500 published by Protegas of Liechtenstein, and also from WO 2022 / 136409 and WO 2022 / 136408, wherein in any of the aforementioned prior art documents, the graft polymers within the general compositions disclosed in the aforementioned publications and also within each individualized specific cleaning composition can be partially or completely replaced by the graft polymers of the present invention having the same function. In those aforementioned documents, various types of formulations for cleaning compositions are also disclosed; all such composition types - general compositions and also each individualized specific cleaning composition - can equally apply to those cleaning compositions contemplated herein.

[0516] Thus, in addition to or as an alternative to such existing prior art compositions containing polymers or any such compounds (which can be replaced by such graft polymers of the present invention) - such alternatives being known to those skilled in the art -, the present invention also encompasses any and all such disclosed compositions that cover the previously mentioned prior art disclosures but further contain at least one of the compounds of the present invention, wherein the content of the graft polymers of the present invention is present in the formulation at a concentration of generally 0.05 wt.% to 20 wt.%, preferably up to 15 wt.%, more preferably up to 10 wt.%, even more preferably up to 5 wt.% and more preferably 0.1 wt.% and even further more preferably 0.5 wt.%, such as preferably from 0.1 wt.% to 5 wt.%, and preferably at a concentration of 0.5 wt.% to 2 wt.% in the case where dye transfer inhibition activity is the main activity.

[0517] Laundry compositions

[0518] The cleaning compositions of the present invention can - and preferably do - contain auxiliary cleaning additives (also abbreviated herein as "auxiliaries"), such auxiliaries preferably being in addition to the surfactant system as previously defined.

[0519] Suitable adjunct cleaning agents include builders, cobuilders, surfactant systems, fatty acids and / or their salts, structurants, thickeners and rheology modifiers, clay / dirt removal / antiredeposition agents, polymeric dirt removal agents, dispersants such as polymeric dispersants, polymeric grease cleaners, solubilizers, amphiphilic copolymers (including those without vinylpyrrolidone), chelating agents, enzymes, enzyme stabilizing systems, encapsulated benefit agents such as encapsulated fragrances, bleaching compounds, bleaches, bleach activators, bleach catalysts, catalytic materials, brighteners, malodor control agents, pigments, dyes, opacifiers, pearlescers, colorants, dye transfer inhibitors, fabric softeners, carriers, foam boosters, foam inhibitors (defoamers), color speckle removers, silver care agents, anti-tarnish agents and / or anti-corrosion agents, sources of alkalinity, pH adjusters, pH buffers, hydrotropes, detergent granules, antibacterial and antimicrobial agents, preservatives, antioxidants, softeners, carriers, fillers, solvents, processing aids, pro-perfumes and fragrances.

[0520] The adjuncts can be present in the composition at levels suitable for the intended use of the composition. Typical levels of use range from as low as 0.001% by weight of the composition of adjuncts such as optical brighteners to 50% by weight of the composition of builders.

[0521] In addition to the surfactant system and the graft polymer, the liquid cleaning composition can additionally - and preferably does - contain at least one of the following: rheology control / modifying agents, emollients, wetting agents, skin rejuvenating actives, and solvents.

[0522] The solid composition can additionally - and preferably does - contain at least one of fillers, bleaches, bleach activators and catalytic materials.

[0523] Suitable examples and levels of use of such cleaning adjuncts are seen in WO 99 / 05242, U.S. Patent Nos. 5,576,282, 6,306,812B1 and 6,326,348B1.

[0524] One of ordinary skill in the art will understand that detersive surfactants encompass any surfactant or mixture of surfactants that provides cleaning, stain removal, or washing benefits to soiled materials.

[0525] Thus, the cleaning compositions of the present invention, such as fabric and home care products, as well as formulations for industrial and institutional cleaning, more particularly such as laundry detergents and hand dishwashing detergents, preferably additionally comprise a surfactant system, and more preferably also comprise additional adjuvants, such as the adjuvants described in more detail above and below.

[0526] The surfactant system may consist of one surfactant, or may consist of a combination of surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. Those of ordinary skill in the art will understand that the surfactant systems for detergents encompass any surfactant or mixture of surfactants that provides cleaning, stain removal, or washing benefits to soiled materials.

[0527] The cleaning compositions of the present invention preferably comprise a surfactant system in an amount sufficient to provide the desired cleaning properties. In some embodiments, the cleaning composition comprises from about 1% to about 70% of the surfactant system, by weight of the composition. In other embodiments, the liquid cleaning composition comprises from about 2% to about 60% of the surfactant system, by weight of the composition. In additional embodiments, the cleaning composition comprises from about 5% to about 30% of the surfactant system, by weight of the composition. The surfactant system may comprise a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof.

[0528] Dishwashing compositions

[0529] In laundry formulations, anionic surfactants typically contribute the largest share of surfactants in such formulations. Thus, preferably, the cleaning compositions of the present invention for use in laundry comprise at least one anionic surfactant and optionally additional surfactants selected from any of the surfactant classes described herein, preferably selected from nonionic surfactants and / or amphoteric surfactants and / or zwitterionic surfactants and / or cationic surfactants.

[0530] Non-limiting examples of anionic surfactants useful herein - which may also be used in combination with more than one surfactant - include C9-C20 linear alkylbenzene sulfonates (LAS), C10-C20 primary, branched, and random alkyl sulfates (AS); C10-C18 secondary (2,3) alkyl sulfates; C10-C18 alkyl alkoxy sulfates (AExS), where x is from 1 to 30; C10-C18 alkyl alkoxy carboxylates containing from 1 to 5 ethoxy units; mid-chain branched alkyl sulfates as discussed in US 6,020,303 and US 6,060,443; mid-chain branched alkyl alkoxy sulfates as discussed in US 6,008,181 and US 6,020,303; modified alkylbenzene sulfonates (MLAS) as discussed in WO 99 / 05243, WO 99 / 05242, and WO 99 / 05244; methyl ester sulfonates (MES); and alpha-olefin sulfonates (AOS).

[0531] Preferred examples of suitable anionic surfactants are the alkali metal salts and ammonium salts of the following: C8-C 12 -alkyl sulfates, C 12 -C 18 -fatty alcohol ether sulfates, C 12 -C 18 -fatty alcohol polyether sulfates, ethoxylated C4-C 12 -sulfuric acid half-esters of alkylphenols (ethoxylated: 3 to 50 mol of ethylene oxide / mol), C 12 -C 18 -alkyl sulfonic acids, C 12 -C 18 sulfofatty acid alkyl esters, e.g. C 12 -C 18 sulfofatty acid methyl esters, C 10 -C 18 -alkylarylsulfonic acids, preferably n-C 10 -C 18 -alkylbenzenesulfonic acids, C 10 -C 18 alkyl alkoxy carboxylates and soaps such as C8-C 24 -carboxylic acids. The alkali metal salts of the above compounds are preferably considered, particularly preferably the sodium salts.

[0532] In one embodiment of the invention, the anionic surfactant is selected from n-C 10 -C 18 -alkylbenzenesulfonic acids and fatty alcohol polyether sulfates, which in the context of the present invention are in particular ethoxylated C 12 -C 18 -alkanols (preferably n-C 12 -C 18-sulfate half - esters of alkanols (ethoxylation: 1 to 50 mol of ethylene oxide / mol).

[0533] In one embodiment of the present invention, it is also possible to use alcohol polyether sulfates derived from branched (i.e., synthetic) C 11 -C 18 -alkanols (ethoxylation: 1 to 50 mol of ethylene oxide / mol).

[0534] Preferably, based on C 12 -C 18 -fatty alcohols or based on branched (i.e., synthetic) C 11 -C 18 -the alkoxylation groups of the two types of alkoxylated alkyl sulfates of alkanols are ethoxylation groups, and the average degree of ethoxylation of any alkoxylated alkyl sulfate is 1 to 5, preferably 1 to 3.

[0535] Preferably, based on a specific overall composition, including other components and water and / or solvents, the laundry detergent formulation of the present invention contains at least 1 wt% to 50 wt%, preferably in the range of greater than or equal to about 2 wt% to less than or equal to about 30 wt%, more preferably in the range of greater than or equal to 3 wt% to less than or equal to 25 wt% and most preferably in the range of greater than or equal to 5 wt% to less than or equal to 25 wt% of one or more of the anionic surfactants as described above.

[0536] In a preferred embodiment of the present invention, the anionic surfactant is selected from C10 - C15 linear alkylbenzene sulfonates, C10 - C18 alkyl ether sulfates having 1 - 5 ethoxy units, and C10 - C18 alkyl sulfates.

[0537] Non - limiting examples of non - ionic surfactants - which can also be used in combination with more than one other surfactant - include: C8 - C18 alkyl ethoxylates, such as those from Shell non - ionic surfactants; those from BASF Ethylene oxide / propylene oxide block alkoxylates; C14-C22 medium-chain branched alkyl alkoxylates, BAEx, where x is from 1 to 30, as discussed in US 6,153,577, US 6,020,303, and US 6,093,856; alkyl polysaccharides, as discussed in U.S. 4,565,647 issued on January 26, 1986; specifically, alkyl polyglycosides, as discussed in US4,483,780 and US 4,483,779; polyhydroxy fatty acid amides, as discussed in US 5,332,528; and ether-terminated poly(oxyalkylated) alcohol surfactants, as discussed in US 6,482,994 and WO 01 / 42408.

[0538] Preferred examples of nonionic surfactants are especially alkoxylated alcohols and alkoxylated fatty alcohols, diblock and multiblock copolymers of ethylene oxide and propylene oxide, and reaction products of sorbitan with ethylene oxide or propylene oxide. In addition, alkylphenol ethoxylates, alkyl glycosides, polyhydroxy fatty acid amides (glucamides). Examples of (additional) amphoteric surfactants are so-called amine oxides.

[0539] Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds having the general formula (A)

[0540]

[0541] where the variables are defined as follows:

[0542] R1 is selected from straight-chain C1-C10-alkyl, preferably ethyl and particularly preferably methyl,

[0543] R2 is selected from C8-C22-alkyl, such as n-C8H17, n-C10H21, n-C12H25, n-C14H29, n-C16H33, or n-C18H37,

[0544] R3 is selected from C1-C10-alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isopentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, or isodecyl,

[0545] m and n are in the range from 0 to 300, where the sum of n and m is at least one.

[0546] Preferably, m is in the range from 1 to 100 and n is in the range from 0 to 30.

[0547] Here, the compound having the general formula (A) can be a block copolymer or a random copolymer, preferably a block copolymer.

[0548] Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds having the general formula (B)

[0549]

[0550] where the variables are defined as follows:

[0551] R 1 identical or different and selected from straight-chain C1-C4-alkyl, preferably identical in each case and being ethyl, and particularly preferably methyl,

[0552] R 4 selected from C6-C 20 -alkyl, especially n-C8H 17 、n-C 10 H 21 、n-C 12 H 25 、n-C 14 H 29 、n-C 16 H 33 、n-C 18 H 37 ,

[0553] a is a number in the range from 0 to 6, preferably from 1 to 6,

[0554] b is a number in the range from 0 to 20, preferably from 4 to 20,

[0555] d is a number in the range from 4 to 25.

[0556] Preferably, at least one of a and b is greater than zero.

[0557] Here, the compound having the general formula (B) can be a block copolymer or a random copolymer, preferably a block copolymer.

[0558] Further suitable nonionic surfactants are selected from diblock and multiblock copolymers consisting of ethylene oxide and propylene oxide. Further suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Alkylphenol ethoxylates or alkylpolyglycosides or polyhydroxy fatty acid amides (glucamides) are likewise suitable. An overview of suitable further nonionic surfactants can be found in EP-A 0 851 023 and DE-A 198 19 187.

[0559] Of course, mixtures of two or more different nonionic surfactants can also be present.

[0560] In a preferred embodiment of the present invention, the nonionic surfactant is selected from C12 / 14 and C16 / 18 fatty alcohol alkoxylates, C13 / 15 oxo alcohol alkoxylates, C13-alkanol alkoxylates, and 2-propylheptanol alkoxylates, each of which has 3-15 ethoxy units, preferably 5-10 ethoxy units, or has 1-3 propoxy units and 2-15 ethoxy units.

[0561] Non-limiting examples of amphoteric surfactants - which can also be used in combination with more than one other surfactant - include: water-soluble amine oxides containing an alkyl moiety having from about 8 to about 18 carbon atoms and two moieties selected from the group consisting of alkyl moieties having from about 1 to about 3 carbon atoms and hydroxyalkyl moieties; and water-soluble sulfoxides containing an alkyl moiety having from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl moieties having from about 1 to about 3 carbon atoms and hydroxyalkyl moieties. See WO 01 / 32816, US 4,681,704 and US 4,133,779. Accordingly, suitable surfactants include so-called amine oxides such as lauryl dimethyl amine oxide ("lauryl amine oxide").

[0562] Preferred examples of amphoteric surfactants are amine oxides. Preferred amine oxides are alkyl dimethyl amine oxides or alkylamidopropyl dimethyl amine oxides, more preferably alkyl dimethyl amine oxides and especially coco dimethyl amine oxide. The amine oxides can have a straight-chain or branched intermediate alkyl moiety. Typical straight-chain amine oxides include water-soluble amine oxides containing an R1 = C8-18 alkyl moiety and two R2 and R3 moieties selected from the group consisting of C1-C3 alkyl groups and C1-C3 hydroxyalkyl groups. Preferably, the amine oxides are characterized by the following formula

[0563] R1-N(R2)(R3)-O

[0564] Wherein R1 is a C8-18 alkyl group, and R2 and R3 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, and 3-hydroxypropyl. The linear amine oxide surfactants can particularly include linear C10-C18 alkyldimethylamine oxides and linear C8-C12 alkoxyethyldihydroxyethylamine oxides. Preferred amine oxides include linear C10, linear C10-C12, and linear C12-C14 alkyldimethylamine oxides. As used herein, "mid-branched" means that the amine oxide has an alkyl moiety having n1 carbon atoms and an alkyl branch on an alkyl moiety having n2 carbon atoms. The alkyl branch is located on the alpha carbon from the nitrogen on the alkyl moiety. This type of branching of the amine oxide is also known in the art as internal amine oxide. The sum of n1 and n2 is from 10 to 24 carbon atoms, preferably from 12 to 20, and more preferably from 10 to 16. The number of carbon atoms (n1) of the one alkyl moiety should be substantially the same as the number of carbon atoms (n2) of the one alkyl branch such that the one alkyl moiety and the one alkyl branch are symmetric. As used herein, "symmetric" means that in at least 50 wt%, more preferably at least 75 wt% to 100 wt% of the mid-branched amine oxides used herein, (n1 - n2) is less than or equal to 5, preferably 4, and most preferably 0 to 4 carbon atoms. The amine oxide further contains two moieties independently selected from C1-C3 alkyl groups, C1-C3 hydroxyalkyl groups, or poly(ethylene oxide) groups having on average from about 1 to about 3 ethylene oxide groups. Preferably, these two moieties are selected from C1-C3 alkyl groups, and more preferably both are selected as C1 alkyl groups.

[0565] In a preferred embodiment of the present invention, the zwitterionic surfactant is selected from C8-C18 alkyl-dimethylamine oxides and C8-C18 alkyl-bis(hydroxyethyl)amine oxides.

[0566] The cleaning composition can also contain zwitterionic surfactants - which can also be used in combination with more than one other surfactant.

[0567] Suitable zwitterionic surfactants include betaines such as alkyl betaines, alkylamidopropyl betaines, amidazolinium betaines, sultaines (INCI Sultaine), and phosphobetaines. Examples of suitable betaines and sultaines are as follows (according to INCI nomenclature): almond amidopropyl betaine, apricot amidopropyl betaine, avocado amidopropyl betaine, babassu amidopropyl betaine, behenamidopropyl betaine, behenyl betaine, erucamidopropyl betaine, capryloyl / capramidopropyl betaine, carnitine, cetyl betaine, cocamidoylethyl betaine, cocamidopropyl betaine, cocamidopropyl hydroxysultaine, coco betaine, coco hydroxysultaine, coco / oleamidopropyl betaine, coco sultaine, decyl betaine, oleyl glycine dihydroxyethyl ester, soy glycine dihydroxyethyl ester, stearyl glycine dihydroxyethyl ester, tallow glycine dihydroxyethyl ester, polydimethylsiloxane propyl PG-betaine, erucamidopropyl hydroxysultaine, hydrogenated tallow betaine, isostearamidopropyl betaine, lauramidopropyl betaine, lauryl betaine, lauryl hydroxysultaine, lauryl sultaine, milkamidopropyl betaine, minkamidopropyl betaine, myristamidopropyl betaine, myristyl betaine, oleamidopropyl betaine, oleamidopropyl hydroxysultaine, oleyl betaine, oliveamidopropyl betaine, palmamidopropyl betaine, palm oil amidopropyl betaine, palmoyl carnitine, palm kernel oil amidopropyl betaine, polytetrafluoroethylene acetoxypropyl betaine, ricinoleamidopropyl betaine, sesame oil amidopropyl betaine, soybean oil amidopropyl betaine, stearamidopropyl betaine, stearyl betaine, tallowamidopropyl betaine, tallowamidopropyl hydroxysultaine, tallow betaine, tallow dihydroxyethyl betaine, undecylenamidopropyl betaine, and wheat germ oil amidopropyl betaine.

[0568] Preferred betaines are, for example, C 12 -C 18 -alkyl betaines and sultaines. The zwitterionic surfactant is preferably a betaine surfactant, more preferably a cocamidopropyl betaine surfactant.

[0569] Non-limiting examples of cationic surfactants - which can also be used in combination with more than one other surfactant - include: quaternary ammonium surfactants which can have up to 26 carbon atoms, including: alkoxylated quaternary ammonium (AQA) surfactants as discussed in US 6,136,769; dimethyl hydroxyethyl quaternary ammonium as discussed in US 6,004,922; dimethyl hydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants as discussed in WO 98 / 35002, WO 98 / 35003, WO 98 / 35004, WO 98 / 35005 and WO 98 / 35006; cationic ester surfactants as discussed in US Patent Nos. 4,228,042, 4,239,660, 4,260,529 and US 6,022,844; and amino surfactants as discussed in US 6,221,825 and WO00 / 47708, specifically amido propyl dimethyl amine (APA).

[0570] The compositions according to the invention can comprise at least one builder. In the context of the present invention, no distinction will be made between builders and such components which are elsewhere referred to as "co-builders". 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 citrate, phosphate, silicate, carbonate, phosphonate, aminocarboxylate and polycarboxylate.

[0571] In the context of the present invention, the term citrate includes the mono-alkali metal salts and di-alkali metal salts of citric acid, and in particular the monosodium salt and preferably the trisodium salt of citric acid, the ammonium salts or substituted ammonium salts of citric acid and citric acid itself. Citrates can be used as anhydrous compounds or as hydrates, for example as sodium citrate dihydrate. The amount of citrate is calculated with reference to anhydrous trisodium citrate.

[0572] The term phosphate includes sodium metaphosphate, sodium orthophosphate, sodium hydrogen phosphate, sodium pyrophosphate and polyphosphates such as sodium tripolyphosphate. However, preferably, the compositions according to the invention are free of phosphates and polyphosphates, with the exception of hydrogen phosphates, for example free of trisodium phosphate, pentasodium triphosphate and hexasodium metaphosphate ("phosphate-free"). With respect to phosphates and polyphosphates, "free of" in the context of the present invention should be understood to mean that the total content of phosphates and polyphosphates is in the range of 10 ppm to 0.2% by weight of the corresponding composition, determined by gravimetry.

[0573] The term carbonate includes alkali metal carbonates and alkali metal hydrogencarbonates, preferably sodium salts. Particularly preferred is Na2CO3.

[0574] Examples of phosphonates are hydroxyalkanephosphonates and aminoalkanephosphonates. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) is particularly important as a builder. It is preferably used as the sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Suitable aminoalkanephosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and also their higher homologues. They are preferably used in the form of neutral reaction sodium salts, for example as the hexasodium salt of EDTMP or as the heptasodium and octasodium salts of DTPMP.

[0575] Examples of aminocarboxylates and polycarboxylates are nitrilotriacetate, ethylenediaminetetraacetate, diethylenetriaminepentaacetate, triethylenetetraminehexaacetate, propylenediaminetetraacetate, ethanol-diglycinate, methylglycinediacetate and glutaminediacetate. The terms aminocarboxylate and polycarboxylate also include their respective unsubstituted or substituted ammonium salts and alkali metal salts, such as sodium salts, in particular the sodium salts of the respective fully neutralized compounds.

[0576] In the context of the present invention, silicates specifically include disodium silicate and sodium metasilicate, aluminosilicates such as zeolites and layered silicates, in particular those having the formulas α-Na2Si2O5, β-Na2Si2O5 and δ-Na2Si2O5.

[0577] The compositions according to the invention may contain one or more builders selected from materials not mentioned above. Examples of builders are α-hydroxypropionic acid and oxidized starch.

[0578] In one embodiment of the invention, the builder is selected from polycarboxylates. The term "polycarboxylate" includes non-polymeric polycarboxylates, such as succinic acid, C2-C 16 -alkyl disuccinates, C2-C 16 -alkenyl disuccinates, ethylenediamine N,N'-disuccinic acid, tartaric acid diacetate, alkali metal malonates, tartaric acid monoacetate, propane tricarboxylic acid, butane tetracarboxylic acid and cyclopentane tetracarboxylic acid.

[0579] Oligomeric or polymeric polycarboxylates are, for example, polyaspartic acid and its alkali metal salts, in particular its sodium salts, (meth)acrylic acid homopolymers and (meth)acrylic acid copolymers and their alkali metal salts, in particular their sodium salts.

[0580] Suitable comonomers are monoethylenically unsaturated dicarboxylic acids, such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid. Suitable polymers are in particular polyacrylic acid, which preferably has a weight average molecular weight M in the range from 2000 to 40 000 g / mol, preferably from 2000 to 10 000 g / mol, in particular from 3000 to 8000 g / mol.w Further suitable copolymer polycarboxylates are in particular those of acrylic acid and methacrylic acid and those of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid or their acid anhydrides such as maleic anhydride. Suitable copolymers are in particular copolymers of acrylic acid and maleic acid with a weight average molecular weight Mw in the range from 2000 to 100,000, preferably from 3000 to 80,000.

[0581] The preferred weight average molecular weight Mw of the polyaspartic acid is in the range between 1000 g / mol and 20,000 g / mol, preferably between 1500 and 15,000 g / mol and particularly preferably between 2000 and 10,000 g / mol.

[0582] It is also possible to use at least one monomer from the group consisting of monoethylenically unsaturated C3-C 10 -mono- or C4-C 10 -dicarboxylic acids or their acid anhydrides (such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid) and copolymers of at least one hydrophilic or hydrophobic modified comonomer as listed below.

[0583] Suitable hydrophobic comonomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins having ten or more carbon atoms or mixtures thereof, such as, for example, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracosene and 1-hexacosene, C 22 -α-olefins, C 20 -C 24 -α-olefins and mixtures of polyisobutene having on average 12 to 100 carbon atoms / molecule.

[0584] Suitable hydrophilic comonomers are monomers having a sulfonate or phosphonate group, and also nonionic monomers having a hydroxyl functional group or an epoxyalkyl group. As examples, mention may be made of: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolybutylene glycol (meth)acrylate, methoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, ethoxypolybutylene glycol (meth)acrylate and ethoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate. Here the polyalkylene glycol may contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units / molecule.

[0585] Particularly preferred monomers containing sulfonic acid groups herein are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 3-methylacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethylacrylamide, sulfomethylmethylacrylamide, and salts of said acids, such as their sodium salts, potassium salts, or ammonium salts.

[0586] Particularly preferred monomers containing phosphonic acid groups are vinylphosphonic acid and its salts.

[0587] Further suitable oligomers or polymeric polycarboxylates include graft polymers of (meth)acrylic acid or maleic acid on polysaccharides such as degraded starch, carboxymethylated polysaccharides such as carboxymethylated cellulose, carboxymethylated inulin, or carboxymethylated starch, or polyepoxysuccinic acid and its alkali metal salts, especially its sodium salts.

[0588] In addition, amphoteric polymers can also be used as builders.

[0589] The composition according to the invention can contain, for example, a total of from 0.1% to 90% by weight, preferably from 5% to 80% by weight, preferably up to 70% by weight of builder, especially in the case of solid formulations. The liquid formulations according to the invention preferably contain from 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 of builder.

[0590] The formulations according to the invention can contain one or more alkaline carriers. For example, if an alkaline pH is desired, the alkaline carrier ensures a pH of at least 9. Suitable are, for example, the alkali metal carbonates, alkali metal hydrogencarbonates, and alkali metal metasilicates mentioned above, and, additionally, alkali metal hydroxides. In each case, the preferred alkali metal is potassium, and particularly preferably sodium. In one embodiment of the invention, the pH > 7 is adjusted by using amines, preferably alkanolamines, more preferably triethanolamine.

[0591] In one embodiment of the invention, the laundry formulation according to the invention additionally contains at least one enzyme.

[0592] The enzymes available are one or more hydrolases selected, for example, from lipases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, peroxidases, and combinations of at least two of the foregoing types.

[0593] Such enzymes can be incorporated at levels sufficient to provide an effective amount for cleaning. Preferred amounts are active enzymes in the range of 0.001% to 5% by weight in the detergent compositions according to the invention. Enzyme stabilization systems can 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 / molecule and dicarboxylic acids having 2 to 6 carbon atoms / 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 their respective sodium and potassium salts.

[0594] Preferably, the at least one enzyme is a detergent enzyme.

[0595] In one embodiment, the enzymes are classified as oxidoreductases (EC 1), transferases (EC 2), hydrolases (EC 3), lyases (EC 4), isomerases (EC 5), or ligases (EC 6). The EC numbers are according to the Enzyme Nomenclature Recommendations of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology (1992), including its supplements published in 1993 - 1999. Preferably, the enzymes are hydrolases (EC 3).

[0596] In a preferred embodiment, the enzyme is selected from the group consisting of

[0597] Proteases, amylases, lipases, cellulases, mannanases, hemicellulases, phospholipases, esterases, pectinases, lactases, peroxidases, xylanases, cutinases, pectate lyases, keratinases, reductases, oxidases, phenol oxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanase, β-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, nucleases, deoxyribonucleases, phosphodiesterases, phytases, carbohydrases, galactanases, xanthanases, xyloglucanases, redox enzymes, perhydrolases, aminopeptidases, asparaginases, carbohydrases, carboxypeptidases, catalases, chitinases, cyclodextrin glycosyltransferases, α-galactosidases, β-galactosidases, glucoamylases, α-glucosidases, β-glucosidases, invertases, ribonucleases, transglutaminases and dispersin, and combinations of at least two of the foregoing types. More preferably, the enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases, mannanases, xylanases, deoxyribonucleases, dispersin, pectinases, redox enzymes and cutinases and combinations of at least two of the foregoing types. Most preferably, the enzyme is a protease, preferably a serine protease, more preferably subtilisin.

[0598] Preferably, the protease is a protease having at least 90% sequence identity with SEQ ID NO:22 of EP 1921147B1 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 WO 2021032881A1.

[0599] The composition of the present invention may comprise one type of enzyme or more than one different type of enzyme, such as amylase and protease, or more than one of the same type of enzyme, such as two or more different proteases, or a mixture thereof, such as amylase and two different proteases.

[0600] The enzyme may be incorporated into the composition at a level sufficient to provide an effective amount for achieving a beneficial effect, preferably for a primary washing effect and / or a secondary washing effect, such as an anti-greying or anti-pilling effect (e.g., in the case of cellulase). Preferably, the enzyme is present in the composition at a level of about 0.00001% to about 5%, preferably about 0.00001% to about 2%, more preferably about 0.0001% to about 1%, or even more preferably about 0.001% to about 0.5% enzyme protein by weight of the composition.

[0601] Preferably, the enzyme-containing composition further comprises an enzyme stabilization system.

[0602] Preferably, the enzyme-containing composition described herein comprises an enzyme stabilization system in an amount of from about 0.001% to about 10%, from about 0.005% to about 8%, or from about 0.01% to about 6% by weight of the composition. The enzyme stabilization system can be any stabilization system that is compatible with the enzyme.

[0603] Preferably, the enzyme stabilization system comprises at least one compound selected from the group consisting of polyols (preferably 1,3-propanediol, ethylene glycol, glycerol, 1,2-propanediol, or sorbitol), inorganic salts (preferably CaCl2, MgCl2, or NaCl), short-chain (preferably C1-C3) carboxylic acids or their salts (preferably formic acid, formates (preferably sodium formate), acetic acid, acetates, or lactates), borates, boric acid, boronic acid (preferably 4-formylphenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde bisulfite adducts. 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, and preferably a combination of one or more compounds selected from the group consisting of borates, boric acid, boronic acid (preferably 4-FPBA), peptide aldehydes, peptide acetals, and peptide aldehyde bisulfite adducts. In particular, if a protease is present in the composition, a protease inhibitor can be added, preferably selected from borates, boric acid, boronic acid (preferably 4-FPBA), peptide aldehydes (preferably peptide aldehydes such as Z-VAL-H or Z-GAY-H), peptide acetals, and peptide aldehyde bisulfite adducts.

[0604] The composition according to the invention can comprise one or more bleaching agents (bleaching agents).

[0605] Preferred bleaching agents are selected from sodium perborate, anhydrous or, for example, as the monohydrate or as the tetrahydrate or the so-called dihydrate, sodium percarbonate, anhydrous or, for example, as the monohydrate, and sodium persulfate, where the term "persulfate" in each case includes salts of the peracid H2SO5 and persulfates.

[0606] In view of this, the alkali metal salts can also be, in each case, alkali metal bicarbonates, alkali metal perborohydrates, and alkali metal persulfates. However, in each case, the dibasic alkali metal salts are preferred.

[0607] The formulations according to the invention may comprise one or more bleach catalysts. The bleach catalysts may be selected from oxaziridinium-based bleach catalysts, bleach-promoting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands as well as also cobalt-, iron-, copper- and ruthenium-amine complexes may also be used as bleach catalysts.

[0608] The formulations according to the invention may comprise one or more bleach activators such as tetraacetylethylenediamine, tetraacetylmethylenediamine, tetraacetylglycoluril, tetraacetylhexanediamine, acylated phenolsulfonates such as n-nonanoyl- or isononanoyloxybenzenesulfonates, N-methylmorpholinium-acetonitrile salt ("MMA salt"), trimethylammonium acetonitrile salt, N-acylimides such as N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine ("DADHT") or nitrile quaternary ammonium (trimethylammonium acetonitrile salt).

[0609] The formulations according to the invention may comprise one or more corrosion inhibitors. In this context, this should be understood to include those compounds which inhibit the corrosion of metals. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazole, bisbenzotriazole, aminotriazole, alkylaminotriazole, and also phenol derivatives such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.

[0610] In one embodiment of the invention, the formulations according to the invention comprise in total corrosion inhibitors in the range from 0.1% to 1.5% by weight.

[0611] The formulations according to the invention may further comprise a cleaning polymer and / or a detergency polymer and / or an anti-greying polymer.

[0612] Additional cleaning polymers may include but are not limited to "multifunctional polyethyleneimine" (e.g., HP20 from BASF) and / or "multifunctional diamine" (e.g., HP96 from BASF). Such multifunctional polyethyleneimines typically have a weight-average molecular weight M in the range from 3000 to 250000, preferably from 5000 to 200000, more preferably from 8000 to 100000, more preferably from 8000 to 50000, more preferably from 10000 to 30000 and most preferably from 10000 to 20000 g / mol wEthoxylated polyethyleneimine. Based on the total weight of the material, suitable polyfunctional polyethyleneimines have ethylene oxide side chains in the range of 80 wt% to 99 wt%, preferably 85 wt% to 99 wt%, more preferably 90 wt% to 98 wt%, most preferably 93 wt% to 97 wt% or 94 wt% to 96 wt%. Ethoxylated polyethyleneimine typically consists of a polyethyleneimine core and a poly(ethylene oxide) shell. Suitable polyethyleneimine core molecules are those having a weight-average molecular weight M in the range of 500 to 5000 g / mol w of polyethyleneimine. A molecular weight of 500 to 1000 g / mol is preferably employed, and even more preferably an M of 600 to 800 g / mol w . Then, the ethoxylated polymer on average has 5 to 50, preferably 10 to 35, and even more preferably 20 to 35 ethylene oxide (EO) units per NH-functional group.

[0613] Suitable polyfunctional diamines are typically ethoxylated C2 to 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 to 10000, more preferably 3000 to 8000, and most preferably 4000 to 6000 g / mol w . In a preferred embodiment of the present invention, ethoxylated hexamethylenediamine, which is additionally quaternized and sulfated, can be used, which on average contains 10 to 50, preferably 15 to 40, and even more preferably 20 to 30 ethylene oxide (EO) groups per NH-functional group, and which preferably bears two cationic ammonium groups and two anionic sulfate groups.

[0614] Suitable additional polyfunctional polyethylenimines, polyfunctional diamines, and oligamines include those claimed in WO 2021 / 254828, WO 2022 / 136408A1, WO 2022 / 136409A1, WO 2021 / 165468, WO 2023 / 021103, WO2023 / 021104, WO 2023 / 021105, and WO 2023 / 117494.

[0615] In a preferred embodiment of the present invention, the cleaning composition may contain at least one polyfunctional polyethyleneimine and / or at least one polyfunctional diamine and / or oligomeric amine, specifically any one of the claimed polymers from WO 2021 / 254828, WO 2022 / 136408A1, WO 2022 / 136409A1, WO 2021 / 165468, WO 2023 / 021103, WO 2023 / 021104, WO 2023 / 021105 and / or WO 2023 / 117494 to improve cleaning performance, such as preferably improving stain removal ability, especially the primary detergency of laundry detergents on particulate stains on polyester fabrics. The polyfunctional polyethyleneimine or polyfunctional diamine or oligomeric amine or a mixture thereof as described above can be added to laundry detergents and cleaning compositions in an amount generally of 0.05 to 15 wt%, preferably 0.1 to 10 wt%, more preferably 0.25 to 5 wt% and even as low as 2 wt% based on the specific overall composition (including other components and water and / or solvent).

[0616] Accordingly, one aspect of the present invention is a laundry detergent composition, particularly a liquid laundry detergent, comprising (i) at least one polymer of the present invention and (ii) at least one compound selected from polyfunctional polyethyleneimines and polyfunctional diamines and oligomeric amines and mixtures thereof.

[0617] In one embodiment of the present invention, the ratio of at least one polymer of the present invention to (ii) at least one compound selected from polyfunctional polyethyleneimines and polyfunctional diamines and oligomeric amines and mixtures thereof is from 10:1 to 1:10, preferably 5:1 to 1:5 and more preferably 3:1 to 1:3.

[0618] Suitable anti-greying polymers include copolymers of acrylic acid or maleic acid and styrene, graft polymers of acrylic acid on maltodextrin or carboxymethylated cellulose and their alkali metal salts, especially their sodium salts.

[0619] Laundry formulations containing the polymers of the present invention may also contain at least one complexing agent.

[0620] Preferred complexing agents are methylglycine diacetic acid (MGDA) and glutamic acid diacetic acid (GLDA) and their salts. Particularly preferred complexing agents are methylglycine diacetic acid and its salts. According to the present invention, the complexing agent is preferably from 1% to 50% by weight (which will be reduced to 20%).

[0621] MGDA and GLDA can be present as racemates or enantiomerically pure compounds. GLDA is preferably selected from L-GLDA or an enantiomer-rich mixture of L-GLDA, in which there is at least 80 mol%, preferably at least 90 mol% of L-GLDA.

[0622] In one embodiment of the present invention, the complexing agent is racemic MGDA. In another embodiment of the present invention, the complexing agent is selected from L-MGDA and the enantiomeric mixture of L- and D-MGDA, wherein L-MGDA is in the majority and wherein the L / D molar ratio is in the range of 55:45 to 95:5, preferably 60:40 to 85:15. The L / D molar ratio can be determined, for example, by polarimetry or chromatographic means, preferably by HPLC with a chiral column, such as a column having cyclodextrin as the stationary phase or an optically active ammonium salt immobilized on the column. For example, an immobilized D-penicillamine salt can be used.

[0623] MGDA or GLDA is preferably used as a salt. Preferred salts are ammonium salts and alkali metal salts, particularly preferably potassium salts and especially sodium salts. These can have, for example, the following general formula (CA I) or (CA II):

[0624] [CH3-CH(COO)-N(CH2-COO)2]Na 3-x-y K x H y (CA I)

[0625] x is in the range of 0.0 to 0.5, preferably up to 0.25,

[0626] y is in the range of 0.0 to 0.5, preferably up to 0.25,

[0627] [OOC-(CH2)2-CH(COO)-N(CH2-COO)2]Na 4-x-y K x H y (CA II)

[0628] x is in the range of 0.0 to 0.5, preferably up to 0.25,

[0629] y is in the range of 0.0 to 0.5, preferably up to 0.25.

[0630] The trisodium salt of MGDA and the tetrasodium salt of GLDA are very particularly preferred.

[0631] Laundry formulations comprising the polymers of the present invention may also comprise at least one antimicrobial agent.

[0632] Antimicrobial agents are chemical compounds that kill microorganisms or inhibit their growth or reproduction. Microorganisms can be bacteria, yeasts or molds. Preservatives are antimicrobial agents that can be added to aqueous products and compositions to maintain the original properties, characteristics and integrity of the products and compositions by killing contaminating microorganisms or inhibiting their growth.

[0633] The composition / formulation may contain one or more antimicrobial agents and / or preservatives as listed on pages 35 to 39 of patent WO 2021 / 115912 A1 (“Formulations comprising a hydrophobically modified polyethyleneimine and one or more enzymes”).

[0634] Of particular interest for cleaning compositions and fabric and household care products and specifically in laundry formulations are any of the following antimicrobial agents and / or preservatives:

[0635] 4,4'-dichloro-2-hydroxy diphenyl ether (other names: 5-chloro-2-(4-chlorophenoxy)phenol, hydroxy dichloro diphenyl ether (Diclosan), DCPP); HP 100 (30 wt.% DCPP in 1,2-propanediol); 2-phenoxyethanol (other names: phenoxyethanol, methylphenyl glycol, phenoxyethanol, ethylene glycol phenyl ether, ethylene glycol monophenyl ether, 2-(phenoxy)ethanol, 2-phenoxy-1-ethanol); 2-bromo-2-nitropropane-1,3-diol (other names: 2-bromo-2-nitro-1,3-propanediol, bronopol); glutaraldehyde (other names: 1,5-pentanedial, pentane-1,5-dial, glutaral, glutardialdehyde); glyoxal (other names: ethanedial, oxylaldehyde, 1,2-ethanedial); 5-bromo-5-nitro-1,3-dioxane (other names: 5-bromo-5-nitro-m-dioxane, ); phenoxypropanol (other names: propylene glycol phenyl ether, phenoxyisopropanol, 1-phenoxy-2-propanol, 2-phenoxy-1-propanol); glucoprotamine (chemical description: reaction product of glutamic acid and alkyl propanediamine, other name: Glucoprotamine 50); cyclohexylhydroxydiazene-1-oxide, potassium salt (other names: N-cyclohexyl-diazene dioxide, potassium HDO, Xyligene); formic acid (other names: methanoic acid, FM, FM 75, FM 85, FM99, FM) and its salts, such as sodium formate); tetrahydro-3,5-dimethyl-1,3,5-thiadiazine-2-thione (other names: 3,5-dimethyl-1,3-5-thiadiazinane-2-thione, Dazomet); 2,4-dichlorobenzyl alcohol (other names: dichlorobenzyl alcohol, 2,4-dichloro-benzyl alcohol, (2,4-dichlorophenyl)-methanol, DCBA); 1-propanol (other names: n-propanol, propan-1-ol, n-propyl alcohol); 1,3,5-tris(2-hydroxyethyl)-hexahydro-1,3,5-triazine (other names: hexahydrotriazine, tris(hydroxyethyl)-hexahydrotriazine, hexahydro-1,3-5-tris(2-hydroxyethyl)-s-triazine, 2,2′,2″-(hexahydro-1,3,5-triazine-1,3,5-triyl)triethanol); 2-butyl-benz[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”); a mixture of 5-chloro-2-methyl-2H-isothiazol-3-one (“CMIT”) and 2-methyl-2H-isothiazol-3-one (“MIT”) (CMIT / MIT mixture); 1,2-benzisothiazol-3(2H)-one (“BIT”); hex-2,4-dienoic acid (common name “sorbic acid”) and its salts, such as calcium sorbate, sodium sorbate; (E,E)-hex-2,4-dienoic acid potassium salt (potassium sorbate); lactic acid and its salts; L-(+)-lactic acid; especially sodium lactate; benzoic acid and salts of benzoic acid, such as sodium benzoate, ammonium benzoate, calcium benzoate, magnesium benzoate, MEA benzoate, 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; dicetyldimethylammonium chloride (“DDAC”); N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine (“diamine”); peracetic acid; hydrogen peroxide.

[0636] At least one antimicrobial or preservative can be added to the composition of the present invention at a concentration of 0.001% to 10% relative to the total weight of the composition.

[0637] 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%.

[0638] The laundry formulation of the present invention can comprise at least one antimicrobial agent from the above list and / or a combination thereof, and / or a combination with at least one other antimicrobial agent not listed herein.

[0639] The formulation according to the invention may also comprise water and / or additional organic solvents, such as ethanol or propylene glycol, and / or fillers such as sodium sulfate.

[0640] Additional optional ingredients may be, but are not limited to, viscosity modifiers, cationic surfactants, foam boosters or defoamers, fragrances, dyes, optical brighteners and dye transfer inhibitors.

[0641] General cleaning compositions and formulations

[0642] Another aspect of the invention is also a dishwashing composition comprising at least one polymer of the invention as described above.

[0643] Accordingly, one aspect of the invention is also the use of the polymer of the invention as described above in dishwashing applications (such as manual or automatic dishwashing applications).

[0644] The dishwashing composition according to the invention may be in the form of a liquid, semi-liquid, cream, lotion, gel, or solid composition, solid embodiments encompassing, for example, powders and tablets. Liquid compositions are typically preferably used for manual dishwashing applications, while solid formulations and sachet formulations (wherein the sachet may also contain solids in addition to liquid components) are typically preferably used for automatic dishwashing compositions; however, in some regions of the world, liquid automatic dishwashing compositions are also used and are therefore of course also encompassed by the term "dishwashing composition".

[0645] The dishwashing composition is intended to be applied directly or indirectly to tableware and metal and glass surfaces, such as beverage and other glasses, beakers, tableware and cooking utensils such as pots and pans, and cutlery such as forks, spoons, knives, etc.

[0646] The method of the invention for cleaning tableware, metal and / or glass surfaces comprises the step of applying the dishwashing cleaning composition, preferably in liquid form, directly or by means of a cleaning tool (i.e., in pure form) to the surface. The composition is applied directly to the surface to be treated and / or to the cleaning device or tool, such as a dishcloth, sponge or dishbrush, etc., without undergoing substantial dilution immediately prior to application. The cleaning device or tool is preferably wet before or after delivering the composition to it. In the method of the invention, the composition may also be applied in diluted form.

[0647] Both pure and diluted application result in excellent cleaning performance, i.e., the formulation of the invention containing at least one polymer of the invention exhibits excellent degreasing properties. Due to the presence of the polymers of the invention, the effort to remove fat and / or oily soil from tableware, metal and / or glass surfaces is reduced, even when the surfactant level used is lower than in conventional compositions.

[0648] Preferably, the composition is formulated to provide excellent grease cleaning (degreasing) properties, long-lasting foam, and / or improved viscosity control upon exposure to reduced temperature; preferably at least two, more preferably all three properties are present in the dishwashing composition of the present invention. Optional - preferably present - additional benefits of the manual dishwashing composition of the present invention include soil removal, brightening, and / or hand care; more preferably at least two and most preferably all three additional benefits are present in the dishwashing composition of the present invention.

[0649] In one embodiment of the present invention, the polymer of the present invention is a component of a manual dishwashing formulation that additionally comprises at least one surfactant, preferably at least one anionic surfactant.

[0650] In another embodiment of the present invention, the polymer of the present invention is a component of a manual dishwashing formulation that additionally comprises at least one anionic surfactant and at least one other surfactant preferably selected from amphoteric surfactants and / or zwitterionic surfactants. In a preferred embodiment of the present invention, the manual dishwashing formulation contains at least one amphoteric surfactant, preferably amine oxide, or at least one zwitterionic surfactant, preferably betaine, or a mixture thereof, to assist in the foaming, detergency, and / or mildness of the detergent composition.

[0651] Examples of suitable anionic surfactants have been mentioned above for laundry compositions.

[0652] Preferred anionic surfactants for dishwashing compositions are selected from C10-C15 linear alkylbenzene sulfonates, C10-C18 alkyl ether sulfates having 1-5 ethoxy units, and C10-C18 alkyl sulfates.

[0653] Preferably, based on the specific overall composition, including other components and water and / or solvent, the manual dishwashing detergent formulation of the present invention comprises at least 1 wt% to 50 wt%, preferably in the range of greater than or equal to about 3 wt% to equal to or less than about 35 wt%, more preferably in the range of greater than or equal to 5 wt% to less than or equal to 30 wt%, and most preferably in the range of greater than or equal to 5 wt% to less than or equal to 20 wt% of one or more anionic surfactants as described above.

[0654] The dishwashing composition according to the present invention may comprise at least one amphoteric surfactant.

[0655] Examples of suitable amphoteric surfactants for dishwashing compositions have been mentioned above for laundry compositions.

[0656] Preferred zwitterionic surfactants for dishwashing compositions are selected from C8-C18 alkyl-dimethylamine oxides and C8-C18 alkyl-bis(hydroxyethyl)amine oxides.

[0657] The manual dishwashing detergent composition of the present invention preferably comprises 1 wt% to 15 wt%, preferably 2 wt% to 12 wt%, more preferably 3 wt% to 10 wt% of the composition of a zwitterionic surfactant, preferably an amine oxide surfactant. Preferably, the composition of the present invention comprises a mixture of an anionic surfactant and an alkyldimethylamine oxide in a weight ratio of less than about 10:1, more preferably less than about 8:1, more preferably about 5:1 to about 2:1.

[0658] The addition of the zwitterionic surfactant provides good foaming properties in the dishwashing composition.

[0659] The dishwashing composition according to the present invention may comprise at least one zwitterionic surfactant.

[0660] Examples of suitable zwitterionic surfactants for dishwashing compositions have been mentioned above for laundry compositions.

[0661] Preferred zwitterionic surfactants for dishwashing compositions are selected from betaine surfactants, more preferably from cocamidopropyl betaine surfactants.

[0662] In a preferred embodiment of the present invention, the zwitterionic surfactant is cocamidopropyl betaine.

[0663] The manual dishwashing detergent composition of the present invention optionally comprises 1 wt% to 15 wt%, preferably 2 wt% to 12 wt%, more preferably 3 wt% to 10 wt% of the composition of a zwitterionic surfactant, preferably a betaine surfactant.

[0664] The dishwashing composition according to the present invention may comprise at least one cationic surfactant.

[0665] Examples of suitable cationic surfactants for dishwashing compositions have been mentioned above for laundry compositions.

[0666] When present in the composition, the cationic surfactant is present in an effective amount, more preferably 0.1 wt% to 5 wt%, preferably 0.2 wt% to 2 wt% of the composition.

[0667] The dishwashing composition according to the present invention may comprise at least one nonionic surfactant.

[0668] Examples of suitable nonionic surfactants for dishwashing compositions have been mentioned above for laundry compositions.

[0669] Preferred nonionic surfactants are condensation products of Guerbet alcohols with 2 to 18 moles, preferably 2 to 15 moles, more preferably 5 - 12 moles of ethylene oxide per mole of alcohol. Other preferred nonionic surfactants for use herein include fatty alcohol polyglycol ethers, alkyl polyglucosides, and fatty acid glucamides.

[0670] The manual dishwashing detergent composition of the present invention may comprise from 0.1 wt% to 10 wt%, preferably from 0.3 wt% to 5 wt%, more preferably from 0.4 wt% to 2 wt% of the composition of a linear or branched C10 alkoxylated nonionic surfactant having an average degree of alkoxylation of 2 to 6, preferably 3 to 5. Preferably, the linear or branched C10 alkoxylated nonionic surfactant is a branched C10 ethoxylated nonionic surfactant having an average degree of ethoxylation of 2 to 6, preferably 3 to 5. Preferably, the composition comprises from 60 wt% to 100 wt%, preferably from 80 wt% to 100 wt%, more preferably 100 wt% of the branched C10 ethoxylated nonionic surfactant based on the total linear or branched C10 alkoxylated nonionic surfactant. The linear or branched C10 alkoxylated nonionic surfactant is preferably a 2-propylheptyl ethoxylated nonionic surfactant having an average degree of ethoxylation of 3 to 5. A suitable 2-propylheptyl ethoxylated nonionic surfactant having an average degree of ethoxylation of 4 is XP40, which is commercially available from BASF SE, Ludwigshafen, Germany. Use of a 2-propylheptyl ethoxylated nonionic surfactant having an average degree of ethoxylation of 3 to 5 results in improved foam levels and long-lasting foam.

[0671] Accordingly, one aspect of the present invention is a detergent composition for manual dishwashing, particularly a liquid detergent composition for manual dishwashing, which comprises (i) at least one polymer of the present invention, and (ii) at least one additional 2-propylheptyl ethoxylated nonionic surfactant having an average degree of ethoxylation of 3 to 5.

[0672] The dishwashing composition according to the present invention may comprise at least one hydrotrope in an effective amount to ensure compatibility of the liquid manual dishwashing detergent composition with water.

[0673] Suitable hydrotropes for use herein include anionic hydrotropes, particularly sodium xylene sulfonate, potassium xylene sulfonate, and ammonium xylene sulfonate, sodium toluene sulfonate, potassium toluene sulfonate, and ammonium toluene sulfonate, sodium isopropylbenzene sulfonate, potassium isopropylbenzene sulfonate, and ammonium isopropylbenzene sulfonate, and mixtures thereof, and related compounds, as disclosed in U.S. Patent 3,915,903.

[0674] The aqueous solubilizing agent of the liquid manual dishwashing detergent composition of the present invention typically comprises from 0.1 wt% to 15 wt%, preferably from 1 wt% to 10 wt%, most preferably from 2 wt% to 5 wt% of the total liquid detergent composition, or a mixture thereof.

[0675] The dishwashing composition according to the present invention may comprise at least one organic solvent.

[0676] Examples of organic solvents are C4-C14 ethers and diethers, diols, alkoxylated diols, C6-C16 diol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated straight-chain C1-C5 alcohols, straight-chain C1-C5 alcohols, amines, C8-C14 alkyl and cycloalkyl hydrocarbons, and halogenated hydrocarbons and mixtures thereof.

[0677] When present, the liquid dishwashing composition will contain from 0.01 wt% to 20 wt%, preferably from 0.5 wt% to 15 wt%, more preferably from 1 wt% to 10 wt%, most preferably from 1 wt% to 5 wt% of the solvent of the liquid detergent composition. These solvents can be used in combination with an aqueous liquid carrier such as water, or they can be used in the absence of any aqueous liquid carrier. At higher solvent systems, the absolute value of the viscosity may decrease, but there is a local maximum point in the viscosity curve.

[0678] The dishwashing composition herein may further comprise from 30 wt% to 90 wt% of an aqueous liquid carrier comprising water, in which other essential and optional ingredients are dissolved, dispersed or suspended. More preferably, the composition of the present invention comprises from 45 wt% to 85 wt%, even more preferably from 60 wt% to 80 wt% of the aqueous liquid carrier. However, the aqueous liquid carrier may contain other materials that are liquid at room temperature (25 °C) or dissolved in the liquid carrier and that may perform some other function in addition to being an inert filler.

[0679] The dishwashing composition according to the present invention may comprise at least one electrolyte.

[0680] Suitable electrolytes are preferably selected from inorganic salts, even more preferably from monovalent salts, most preferably sodium chloride.

[0681] The liquid manual dishwashing composition according to the present invention may comprise from 0.1 wt% to 5 wt%, preferably from 0.2 wt% to 2 wt% of the electrolyte of the composition.

[0682] The manual dishwashing formulation comprising the polymer of the present invention may further comprise at least one antimicrobial agent.

[0683] Examples of suitable antimicrobial agents for dishwashing compositions have been mentioned above for laundry compositions.

[0684] The antimicrobial agent can be added to the manual dishwashing composition of the present invention at a concentration of from 0.0001 wt% to 10 wt% relative to the total weight of the composition. Preferably, the formulation contains 2-phenoxyethanol at a concentration of from 0.01 wt% to 5 wt%, more preferably from 0.1 wt% to 2 wt% and / or 4,4'-dichlor-2-hydroxy-diphenyl ether at a concentration of from 0.001 wt% to 1 wt%, more preferably from 0.002 wt% to 0.6 wt% (in all cases relative to the total weight of the composition).

[0685] Additional ingredients are, such as but not limited to, conditioning polymers, cleaning polymers, surface-modifying polymers, soil flocculating polymers, rheology-modifying polymers, enzymes, structurants, builders, chelating agents, cyclic diamines, emollients, wetting agents, skin-renewing actives, carboxylic acids, washing granules, bleaches and bleach activators, fragrances, malodor control agents, pigments, dyes, opacifiers, beads, pearlescent particles, microcapsules, antibacterial agents, pH regulators including NaOH and alkanolamines such as monoethanolamine and buffering means.

[0686] Ingredients

[0687] Since the polymers of the present invention are biodegradable and, in particular, cleaning formulations typically have a pH of about 7 or higher and often additionally contain enzymes - which are included in such cleaning formulations to degrade biodegradable substances such as fats, proteins, polysaccharides, etc. present in the stains and soils to be removed by the cleaning composition - several factors need to be considered for formulating those biodegradable polymers of the present invention. Such suitable formulations are known in principle and include formulations in solid form - where the enzyme and the polymer can be separated by coating or added into separate granules which are then mixed - as well as formulations in liquid and semi-liquid form, where the polymer and the enzyme can be separated by formulating them in different compartments (such as different compartments of a multi-compartment pouch or bottle having different chambers), where the liquids are poured out simultaneously from the compartments in a predetermined amount to ensure that each component in each chamber is applied in the appropriate amount at each individual point of use. Such multi-compartment pouches and bottles, etc. are also known to the person skilled in the art.

[0688] In addition to all other ingredients mentioned, the liquid formulations disclosed in this section may also contain from 0% to 2%, preferably about 1% of 2-phenoxyethanol.

[0689] The liquid formulations disclosed above and below may contain from 0 - 0.2%, preferably about 0.15%, of 4,4'-dichlor-2-hydroxy-diphenylether, and all the other ingredients mentioned. In addition to all the other ingredients mentioned, the solid laundry compositions without bleach may also contain from 0% - 0.2%, preferably about 0.15%, of 4,4'-dichlor-2-hydroxy-diphenylether.

[0690] The formulations disclosed in this section may also - in addition to all the other ingredients mentioned - contain one or more enzymes selected from those disclosed above, more preferably protease and / or amylase, wherein even more preferably the protease is a protease having at least 90% sequence identity with SEQ ID NO:22 of EP 1921147B1 and having the amino acid substitution R101E (numbering according to BPN), and wherein the amylase is an amylase having at least 90% sequence identity with SEQ ID NO:54 of WO 2021032881A1, and such enzymes are preferably present in the formulation at a level of from about 0.00001% to about 5%, preferably from about 0.00001% to about 2%, more preferably from about 0.0001% to about 1%, or even more preferably from about 0.001% to about 0.5% enzyme protein, by weight of the composition.

[0691] The following compositions shown below (including those in the tables) disclose certain types of general cleaning compositions corresponding to typical compositions related to typical washing conditions typically employed in various regions and countries of the world. The at least one polymer of the present invention can be added to such formulations in a suitable amount as outlined herein.

[0692] When the shown composition does not contain the graft polymer of the present invention, such a composition is a comparative composition. When it contains the graft polymer of the present invention, especially in an amount within the ranges described as preferred, more preferred, etc. herein, such a composition is considered to fall within the scope of the present invention.

[0693] In a preferred embodiment, the graft polymer according to the present invention is used in a laundry detergent.

[0694] The liquid laundry detergent according to the present invention consists of:

[0695] 0.05% - 20% of at least one polymer of the present invention

[0696] 1% - 50% surfactant

[0697] 0.1% - 40% builder, cobuilder and / or chelating agent

[0698] 0.1% - 50% other adjuvants

[0699] Up to a total of 100% water.

[0700] The preferred liquid laundry detergent according to the invention consists of:

[0701] 0.5% - 15% of at least one polymer according to the invention

[0702] 5% - 40% of an anionic surfactant selected from C10 - C15 - LAS and C10 - C18 alkyl ether sulfates containing 1 - 5 ethoxy - units

[0703] 1.5% - 10% of a non - ionic surfactant selected from C10 - C18 - alkyl ethoxylates containing 3 - 10 ethoxy - units

[0704] 2% - 20% of a soluble organic builder / cobuilder selected from C10 - C18 fatty acids, di - and tricarboxylic acids, hydroxy - dicarboxylic and hydroxytricarboxylic acids, aminopolycarboxylates, and polycarboxylic acids

[0705] 0.05% - 5% of an enzyme system containing at least one enzyme suitable for detergent use and preferably also an enzyme stabilization system

[0706] 0.5% - 20% of a mono - alcohol or di - alcohol selected from ethanol, isopropanol, ethylene glycol, or propylene glycol

[0707] 0.1% - 20% of other auxiliaries

[0708] Up to a total of 100% water.

[0709] The solid laundry detergent (such as powder, granule or tablet) according to the invention consists of:

[0710] 0.2% - 20% of at least one polymer according to the invention

[0711] 1% - 50% of a surfactant

[0712] 0.1% - 90% of a builder, cobuilder and / or chelating agent

[0713] 0% - 50% of a filler

[0714] 0% - 40% of a bleaching active substance

[0715] 0.1% - 30% of other auxiliaries and / or water

[0716] where the sum of these components totals 100%.

[0717] The preferred solid laundry detergent according to the invention consists of:

[0718] 0.5% - 10% of at least one polymer according to the invention

[0719] 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

[0720] 1.5% - 7.5% of a nonionic surfactant selected from C10 - C18 - alkyl ethoxylates containing 3 - 10 ethoxy units

[0721] 20% - 80% of an inorganic builder and filler selected from sodium carbonate, sodium bicarbonate, zeolite, soluble silicate, and sodium sulfate

[0722] 0.5% - 15% of a co - builder selected from C10 - C18 fatty acids, di - and tricarboxylic acids, hydroxy - dicarboxylic acids and hydroxy - tricarboxylic acids, aminopolycarboxylates, and polycarboxylic acids

[0723] 0.1% - 5% of an enzyme system containing at least one enzyme suitable for detergent use and preferably also an enzyme stabilization system

[0724] 0.5% - 30% of a bleaching active substance

[0725] 0.1% - 20% of other adjuvants

[0726] Up to a total of 100% of water

[0727] In a preferred embodiment, the polymer according to the invention is used in a detergent for manual dishwashing.

[0728] The liquid manual dishwashing detergent according to the invention consists of:

[0729] 0.05% - 10% of at least one polymer according to the invention

[0730] 1% - 50% of a surfactant

[0731] 0.1% - 50% of other adjuvants

[0732] Up to a total of 100% of water.

[0733] The preferred liquid manual dishwashing detergent according to the invention consists of:

[0734] 0.2% - 5% of at least one polymer according to the invention

[0735] 5% - 40% of an anionic surfactant selected from C10 - C15 - LAS, C10 - C18 alkyl ether sulfates containing 1 - 5 ethoxy units, and C10 - C18 alkyl sulfates

[0736] 2 - 10% of cocamidopropyl betaine

[0737] 0%-10% lauryldimethylamine oxide

[0738] 0%-2% nonionic surfactant, preferably C10-Guerbet alcohol alkoxylate

[0739] 0%-5% enzyme, preferably amylase, and preferably also an enzyme stabilization system

[0740] 0.5%-20% monoalcohol or diol selected from ethanol, isopropanol, ethylene glycol, or propylene glycol

[0741] 0.1%-20% other adjuvants

[0742] up to a total of 100% water

[0743] General formulation of the laundry detergent composition according to the invention:

[0744] (Values: wt%)

[0745] Range of ingredients in the liquid frame formulation Linear alkylbenzene sulfonic acid 0 to 30 Coconut fatty acid 1 to 12 Fatty alcohol ether sulfate 0 to 25 NaOH or mono- or triethanolamine To reach pH 7.5 to pH 9.0 Alcohol ethoxylate 3 to 10 1,2 - propylene glycol 1 to 10 Ethanol 0 to 4 Sodium citrate 0 to 8 Water Up to 100 Example section

[0746] Liquid laundry frame formulation according to the invention:

[0747]

[0748]

[0749] Liquid laundry frame formulation according to the invention - continued:

[0750]

[0751] Laundry powder frame formulation according to the invention:

[0752]

[0753] Laundry powder frame formulation according to the invention - continued:

[0754]

[0755]

[0756] The following three tables show additional typical liquid detergent formulations LD1, LD2, and LD3: (Values: wt.% active substance) Liquid detergent 1 - LD1 "excellent" detergent;

[0757]

[0758] Liquid detergent 2 - LD2 "medium" performance detergent

[0759]

[0760] Liquid detergent 3-LD3 "medium" performance "bio-based" detergent

[0761]

[0762] All three previous tables for LD1, LD2, LD3: * "Graft polymer" = (polyethylene glycol with Mn 6000 g / mol as the grafting matrix, grafted with 40 wt% vinyl acetate (based on the total polymer weight; produced according to the general disclosure of WO2007138054A1)).

[0763] Liquid manual dishwashing frame formulation according to the invention:

[0764]

[0765] Preferably, in the corresponding laundry detergent, cleaning composition, and / or fabric and home care product, at least one graft polymer is present in a concentration, relative to the total weight of such a composition or product, of about 0.01% to about 20%, preferably about 0.05% to 15%, more preferably about 0.1% to about 10%, and most preferably about 0.5% to about 5% by weight, and all values between and including all ranges, all of these ranges being generated by selecting any one of the lower limit values mentioned and further including 0.2, 0.3, 0.4, 1, 1.5, 2, 2.5, 3, 3.5, and 4 and combining it with any one of the upper limit values mentioned and including 19, 18, 17, 16, 14, 13, 12, 11, 9, 8, 7, and 6.

[0766] When the graft polymer of the present invention is used only as a dye transfer inhibitor within a cleaning formulation and more specifically in a laundry detergent, more preferably a liquid laundry detergent, the amount employed is different from that shown in the general and specific formulas presented in this chapter and is as follows:

[0767] At least one graft polymer as described herein and / or the at least one graft polymer obtainable or obtained by the process of the invention as detailed previously - when acting solely as a dye transfer inhibitor - is present in the compositions and products of the invention in a concentration of from about 0.05% to about 20%, preferably from 0.05% to 10%, more preferably from about 0.1% to 8%, even more preferably from about 0.2% to about 6% and still more preferably from about 0.2% to about 4% and most preferably in an amount up to 2%, each by weight % relative to the total weight of such composition or product, and further includes all ranges resulting from selecting any lower limit and any upper limit and all numbers between the mentioned lower and upper limits.

[0768] The present invention encompasses the specific embodiments described throughout this disclosure as part of the invention; the various additional options disclosed in this specification as "optional", "preferred", "more preferred", "even more preferred" or "most preferred" options of a specific embodiment can be selected individually and independently (unless such independent selection is not possible due to the nature of the feature or if such independent selection is explicitly excluded), and then combined within any other embodiment (where other such options and preferences can also be selected individually and independently), where each and any and all such possible combinations are included as separate embodiments as part of the invention.

[0769] The following examples should further illustrate the invention without limiting the scope of the invention.

[0770] Structure of the main chain

[0771] The number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity Mw / Mn of the graft polymers of the invention can be determined by gel permeation chromatography in dimethylacetamide. The mobile phase (eluent) to be used is dimethylacetamide containing 0.5 wt% LiBr. The concentration of the graft polymer in tetrahydrofuran is 4.0 mg / mL. After filtration (pore size 0.2 μm), 100 μL of this solution is injected into the GPC system. Four columns (heated to 60 °C) can be used for separation (PLgel pre-column, 3 PLgel MIXED-E columns). The GPC system is operated at a flow rate of 1 mL / min. DRIAgilent 1100 can be used as the detection system. Poly(ethylene glycol) (PEG) standards (PL) with a molecular weight Mn of from 106 to 1 378 000 g / mol can be used for calibration.

[0772] Unless "Mw" or "Mn" is specified, the molecular weights given in the tables are calculated molecular weights based on the total molar amount of the components used in the preparation reaction. Since those reactions proceed essentially to completion, this is an acceptable way to calculate the molecular weight

[0773] Prepare the following main chains as the main chains of the graft polymers for the present invention; the abbreviations of their structures are:

[0774] Brief description of the structure 35EO + 3CL + 9EO + 3CL + 35EO A 3CL + 34EO + 3CL B 51EO + 3CL + 9EO + 3CL + 51EO C 3CL + 78EO + 3CL D 1.5CL + 34EO + 1.5CL E 5CL + 61EO + 5CL F 1.5CL + 611EO + 1.5CL G 23EO + 4CL + neopentyl glycol + 4CL + 23EO H 20EO / 2PO + 4CL + neopentyl glycol + 4CL + 20EO / 2PO I 20EO + 1CL + neopentyl glycol + 1CL + 20EO J [Random-(3-caprolactone + 35EO)] + 9EO + [Random-(3-caprolactone + 35EO)] K Figure 1

[0775] General synthetic conceptions of main chains A, C, H, I, and J:

[0776] Oligomerize caprolactone before the polymerization of alkylene oxide to obtain a mixed random / block structure, and obtain the main chain by alkoxylation of polycaprolactone. Starter molecules (such as neopentyl glycol, "NPG" in the case of main chains I and J) can be used.

[0777]

[0778] General synthetic conceptions of main chains B, D, E, F, G:

[0779] Add caprolactone after the polymerization of alkylene oxide to obtain a block structure of polycaprolactone-polyalkylene oxide-polycaprolactone

[0780]

[0781] General synthetic conception of main chain K:

[0782] React a suitable starter with a pre-mixed combination of alkylene oxide and caprolactone.

[0783]

[0784] Synthesis of graft polymers 1-21 of the present invention:

[0785] The graft polymers 1-21 of the present invention are synthesized based on main chains A-J.

[0786]

[0787] Note:

[0788] VAc = vinyl acetate; VL = vinyl laurate; VP = vinyl pyrrolidone;

[0789] *Partially hydrolyzed: 40 mol% hydrolysis based on the total amount of VAc.

[0790] (Note: In the case of a deviation between the main chain description in the table and the synthesis description in the following text, the following description shall prevail.)

[0791] Example 1 (Invention 1)

[0792] Example 1a: Polyethylene glycol (molecular weight 400 g / mol) modified with 6 moles of caprolactone

[0793] In a 4-necked flask equipped with a thermometer, a reflux condenser, a nitrogen inlet, a dropping funnel, and a stirrer, 240.0 g of polyethylene glycol (molecular weight 400 g / mol) and 0.75 g of tin(II) 2-ethylhexanoate were placed and heated to 100 °C.

[0794] 415.0 g of ε-caprolactone was added within 15 minutes. The reaction mixture was heated to 160 °C and stirred under nitrogen at 160 °C for 14 hours. After cooling to room temperature, 645.0 g of an orange oil was obtained. 1H-NMR in MeOD 1 indicated a 99.5% conversion of caprolactone.

[0795] Example 1b (main chain A): Polyethylene glycol (molecular weight 400 g / mol) modified with 6 moles of caprolactone and ethoxylated with 70 moles of ethylene oxide

[0796] In a 2 l autoclave, 271.2 g of polyethylene glycol (molecular weight 400 g / mol) modified with 6 moles of caprolactone (Example 1a) and 2.1 g of potassium tert-butoxide were placed and the mixture was heated to 80 °C. The vessel was purged with nitrogen three times and the mixture was heated to 140 °C. 770.9 g of ethylene oxide was added within 14 hours. To complete the reaction, the mixture was allowed to post-react at 140 °C for an additional 5 hours. The reaction mixture was stripped with nitrogen and the volatile compounds were removed in vacuo at 80 °C. After filtration, 1041.0 g of a light brown solid was obtained. 1H-NMR in CDCl3 confirmed the expected structure.

[0797] Example 1c (graft polymer)

[0798] First, the main chain A (455.00 g) was charged into a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere and heated to 90 °C. Feed 1 (2.81 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 24.76 g of tripropylene glycol) and Feed 2 (245.00 g of vinyl acetate) starting 10 min after Feed 1 were started and metered into the stirred vessel at a variable feed rate for Feed 1 (0:00 h to 00:10 h: 9.20 g / h and 00:10 h to 06:10 h: 4.34 g / h) and a constant feed rate for Feed 2 (00:10 h to 06:10 h: 40.8 g / h). After the completion of Feed 1 and Feed 2, Feed 3 (1.79 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 15.72 g of tripropylene glycol) was metered in at a constant feed rate at 90 °C within 0:56 h. After the complete addition of the feeds, the mixture was stirred at 90 °C for 1:00 h. The polymerization mixture was heated to 95 °C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 745 g of a polymer solution.

[0799] Example 2 (of the second invention)

[0800] First, 450.00 g of main chain A was charged into a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere and heated to 90 °C. Feed 1 (10.08 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 36.89 g of tripropylene glycol) and Feed 2 (450.50 g of vinyl acetate) starting 10 min after the start of Feed 1 were initiated and metered into the stirred vessel at a variable feed rate of Feed 1 (0:00 h to 00:10 h: 15.7 g / h and 00:10 h to 06:10 h: 7.39 g / h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 75.0 g / h). After the completion of Feed 1 and Feed 2, Feed 3 (3.19 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 11.66 g of tripropylene glycol) was metered in at a constant feed rate at 90 °C within 0:56 h. After the complete addition of the feeds, the mixture was stirred at 90 °C for 1:00 h. The polymerization mixture was heated to 95 °C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 961 g of a polymer solution.

[0801] Example 3 (of the third invention)

[0802] Example 3a (main chain C): Polyethylene glycol (molecular weight 400 g / mol) modified with 6 moles of caprolactone and ethoxylated with 102.2 moles of ethylene oxide

[0803] In a 2 l autoclave, 192.9 g of polyethylene glycol (molecular weight 400 g / mol) modified with 6 moles of caprolactone (Example 1a) and 2.0 g of potassium tert-butoxide were placed, and the mixture was heated to 80 °C. The vessel was purged with nitrogen three times and the mixture was heated to 140 °C. 801.8 g of ethylene oxide was added within 14 hours. To complete the reaction, the mixture was allowed to post-react at 140 °C for an additional 5 hours. The reaction mixture was stripped with nitrogen and the volatile compounds were removed under vacuum at 80 °C. After filtration, 990.0 g of a light brown solid was obtained. 1H-NMR in CDCl3 confirmed the expected structure.

[0804] Example 3b (grafted polymer):

[0805] First, under a nitrogen atmosphere, main chain C (455.00 g) was charged into a polymerization vessel equipped with a stirrer and a reflux condenser and heated to 90 °C. Feed 1 (2.81 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 24.76 g of tripropylene glycol) and, 10 min after the start of Feed 1, Feed 2 (245.00 g of vinyl acetate) were started and metered into the stirred vessel at a variable feed rate for Feed 1 (0:00 h to 00:10 h: 9.20 g / h and 00:10 h to 06:10 h: 4.34 g / h) and a constant feed rate for Feed 2 (00:10 h to 06:10 h: 40.8 g / h). After completion of Feed 1 and Feed 2, Feed 3 (1.79 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 15.72 g of tripropylene glycol) was metered in at a constant feed rate at 90 °C over 0:56 h. After complete addition of the feeds, the mixture was stirred at 90 °C for 1:00 h. The polymerization mixture was heated to 95 °C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 745 g of a polymer solution.

[0806] Example 4 (invention 4)

[0807] First, under a nitrogen atmosphere, main chain C (400.00 g) was charged into a polymerization vessel equipped with a stirrer and a reflux condenser and heated to 90 °C. Feed 1 (7.24 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 31.90 g of tripropylene glycol) and, 10 min after the start of Feed 1, Feed 2 (600.00 g of vinyl acetate) were started and metered into the stirred vessel at a variable feed rate for Feed 1 (0:00 h to 00:10 h: 13.1 g / h and 00:10 h to 06:10 h: 5.13 g / h) and a constant feed rate for Feed 2 (00:10 h to 06:10 h: 83.4 g / h). After completion of Feed 1 and Feed 2, Feed 3 (4.80 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 21.12 g of tripropylene glycol) was metered in at a constant feed rate at 90 °C over 0:56 h. After complete addition of the feeds, the mixture was stirred at 90 °C for 1:00 h. The polymerization mixture was heated to 95 °C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 1065 g of a polymer solution.

[0808] Example 5 (invention 5)

[0809] Example 5a: Polyethylene glycol ethoxylated with 44 moles of ethylene oxide (molecular weight 1500 g / mol)

[0810] In a 2 l autoclave, 599.9 g of polyethylene glycol (molecular weight 1500 g / mol) and 2.7 g of potassium tert-butoxide were placed, and the mixture was heated to 80 °C. The vessel was purged three times with nitrogen and the mixture was heated to 140 °C. 754.2 g of ethylene oxide were added over 14 hours. To complete the reaction, the mixture was allowed to post-react for an additional 5 hours at 140 °C. The reaction mixture was stripped with nitrogen and the volatile compounds were removed under vacuum at 80 °C. After filtration, 1350.0 g of a light brown solid were obtained. 1H-NMR in CDCl3 confirmed the expected structure.

[0811] Example 5b (main chain D): Polyethylene glycol (molecular weight 1500 g / mol) ethoxylated with 44 moles of ethylene oxide and modified with 6 moles of ε-caprolactone

[0812] In a 4-necked vessel equipped with a thermometer, reflux condenser, nitrogen inlet, dropping funnel and stirrer, 1044.1 g of polyethylene glycol (molecular weight 1500 g / mol) ethoxylated with 44 moles of ethylene oxide (Example 5a) and 1.25 g of tin(II) ethylhexanoate were placed and heated to 90 °C.

[0813] 205.5 g of ε-caprolactone were added over 15 minutes. The reaction mixture was heated to 160 °C and stirred under nitrogen at 160 °C for 10 hours. After cooling to room temperature, 1236.0 g of an orange oil were obtained. 1 H-NMR indicated a 98.8% conversion of caprolactone.

[0814] Example 5c (graft polymer)

[0815] First, the main chain D (455.00 g) was charged into a polymerization vessel equipped with a stirrer and reflux condenser under a nitrogen atmosphere and heated to 90 °C. Feed 1 (2.81 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 24.76 g of tripropylene glycol) and Feed 2 (245.00 g of vinyl acetate) starting 10 min after Feed 1 were initiated and metered into the stirred vessel at a variable feed rate for Feed 1 (0:00 h to 00:10 h: 9.20 g / h and 00:10 h to 06:10 h: 4.34 g / h) and a constant feed rate for Feed 2 (00:10 h to 06:10 h: 40.8 g / h). After completion of Feed 1 and Feed 2, Feed 3 (1.79 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 15.72 g of tripropylene glycol) was metered in at a constant feed rate at 90 °C over 0:56 h. After complete addition of the feeds, the mixture was stirred at 90 °C for 1:00 h. The polymerization mixture was heated to 95 °C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 745 g of a polymer solution.

[0816] Example 6 (invention 6)

[0817] First, under a nitrogen atmosphere, the main chain D (679.00 g) was charged into a polymerization vessel equipped with a stirrer and a reflux condenser and heated to 90 °C. Feed 1 (10.87 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 39.76 g of tripropylene glycol) and, 10 min after the start of Feed 1, Feed 2 (a mixture of 242.50 g of vinyl acetate and 48.50 g of vinyl laurate) were started and metered into the stirred vessel at a variable feed rate for Feed 1 (0:00 h to 00:10 h: 16.9 g / h and 00:10 h to 06:10 h: 7.97 g / h) and a constant feed rate for Feed 2 (00:10 h to 06:10 h: 48.5 g / h). After the completion of Feed 1 and Feed 2, Feed 3 (3.43 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 12.56 g of tripropylene glycol) was metered in at a constant feed rate at 90 °C over 0:56 h. After the complete addition of the feeds, the mixture was stirred at 90 °C for 1:00 h. The polymerization mixture was heated to 95 °C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 1036 g of a polymer solution.

[0818] Example 7 (invention 7)

[0819] Example 7a (main chain E): Polyethylene glycol (molecular weight 1500 g / mol) modified with 3 moles of epsilon-caprolactone

[0820] In a 4-necked vessel equipped with a thermometer, a reflux condenser, a nitrogen inlet, a dropping funnel, and a stirrer, 480.0 g of polyethylene glycol (molecular weight 1500 g / mol) and 0.6 g of tin(II) ethylhexanoate were placed and heated to 80 °C.

[0821] 109.6 g of ε-caprolactone was added over 5 minutes. The reaction mixture was heated to 160 °C and stirred under nitrogen at 160 °C for 10 h. After cooling to room temperature, 580.0 g of an orange oil was obtained. The 1 1H-NMR in CDCl3 indicated a 96.7% conversion of caprolactone

[0822] Example 7b (grafted polymer)

[0823] First, 540.00 g of main chain E was charged into a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere and heated to 90 °C. Feed 1 (7.56 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 27.67 g of tripropylene glycol) and, 10 min after the start of Feed 1, Feed 2 (135.00 g of vinyl acetate) were started and metered into the stirred vessel at a variable feed rate for Feed 1 (0:00 h to 00:10 h: 11.8 g / h and 00:10 h to 06:10 h: 5.55 g / h) and a constant feed rate for Feed 2 (00:10 h to 06:10 h: 22.5 g / h). After completion of Feed 1 and Feed 2, Feed 3 (2.39 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 8.74 g of tripropylene glycol) was metered in at a constant feed rate at 90 °C over 0:56 h. After complete addition of the feeds, the mixture was stirred at 90 °C for 1:00 h. The polymerization mixture was heated to 95 °C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 721 g of a polymer solution.

[0824] Example 8 (invention 8)

[0825] Example 8a: Polyethylene glycol ethoxylated with 47.2 moles of ethylene oxide (molecular weight 600 g / mol)

[0826] In a 2 l autoclave, 222.5 g of polyethylene glycol (molecular weight 600 g / mol) and 2.0 g of potassium tert-butoxide were placed and the mixture was heated to 80 °C. The vessel was purged with nitrogen three times and the mixture was heated to 130 °C. 770.0 g of ethylene oxide was added over 10 h. To complete the reaction, the mixture was allowed to post-react at 140 °C for a further 5 h. The reaction mixture was stripped with nitrogen and the volatile compounds were removed in vacuo at 80 °C. After filtration, 990.0 g of a light brown solid (hydroxyl value: 45.8 mg KOH / g) was obtained.

[0827] Example 8b (main chain F): Polyethylene glycol ethoxylated with 47.2 moles of ethylene oxide and modified with 10 moles of caprolactone (molecular weight 600 g / mol)

[0828] In a 4-necked vessel equipped with a thermometer, a reflux condenser, a nitrogen inlet, a dropping funnel and a stirrer, 617.9 g of polyethylene glycol ethoxylated with 47.2 moles of ethylene oxide (molecular weight 600 g / mol) (Example 8a) and 0.9 g of tin(II) ethylhexanoate were placed and heated to 80 °C.

[0829] Add 288.8 g of ε-caprolactone within 15 minutes. Heat the reaction mixture to 160 °C and stir for 12 hours at 160 °C under nitrogen. After cooling to room temperature, 900.0 g of orange oil is obtained. The 1 1H-NMR in CDCl3 indicates a 99.0% conversion of caprolactone.

[0830] Example 8c (graft polymer)

[0831] First, charge the main chain F (397.29 g) into a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere and heat to 90 °C. Let Feed 1 (3.16 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 35.56 g of propane-1,2-diol) and Feed 2 (238.37 g of vinyl acetate) 10 min after the start of Feed 1 and Feed 3 (158.92 g of N-vinylpyrrolidone) start simultaneously and are metered into the stirred vessel at a variable feed rate for Feed 1 (0:00 h to 00:10 h: 12.9 g / h and 00:10 h to 06:10 h: 6.09 g / h) and constant feed rates for Feed 2 (00:10 h to 06:10 h: 39.7 g / h) and Feed 3 (00:10 h to 06:10 h: 26.5 g / h). After the completion of Feed 1, Feed 2, and Feed 3, Feed 4 (2.03 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 22.80 g of propane-1,2-diol) is metered in at a constant feed rate at 90 °C within 0:56 h. After complete addition of the feeds, the mixture is stirred at 90 °C for 1:00 h. The polymerization mixture is heated to 95 °C and a vacuum of 500 mbar is applied to remove volatiles. The yield is 721 g of a polymer solution.

[0832] Example 9 (Invention 9)

[0833] First, 50.00 g of main chain F was charged into a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere and heated to 90 °C. Feed 1 (1.12 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 4.10 g of tripropylene glycol) and, 10 min after the start of Feed 1, Feed 2 (50.00 g of vinyl acetate) were started and metered into the stirred vessel at a variable feed rate for Feed 1 (0:00 h to 00:10 h: 1.74 g / h and 00:10 h to 06:10 h: 0.82 g / h) and a constant feed rate for Feed 2 (00:10 h to 06:10 h: 8.33 g / h). After Feed 1 and Feed 2 were completed, Feed 3 (0.35 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 1.30 g of tripropylene glycol) was metered in at a constant feed rate at 90 °C over 0:56 h. After complete addition of the feeds, the mixture was stirred at 90 °C for 1:00 h. The polymerization mixture was heated to 95 °C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 107 g of a polymer solution

[0834] Example 10 (invention 10)

[0835] Example 10a:

[0836] Polyethylene glycol (molecular weight 600 g / mol) ethoxylated with 47.2 moles of ethylene oxide and modified with 3 moles of caprolactone (main chain G) was placed in a 4-necked vessel equipped with a thermometer, a reflux condenser, a nitrogen inlet, a dropping funnel, and a stirrer. 669.8 g of polyethylene glycol (molecular weight 600 g / mol) ethoxylated with 47.2 moles of ethylene oxide (Example 8a) and 0.8 g of tin(II) ethylhexanoate were heated to 80 °C.

[0837] 85.6 g of ε-caprolactone was added over 15 minutes. The reaction mixture was heated to 160 °C and stirred under nitrogen at 160 °C for 12 hours. After cooling to room temperature, 746.0 g of an orange solid was obtained. In 1 1H-NMR in CDCl3 indicated a 98.0% conversion of caprolactone.

[0838] Example 10b (graft polymer)

[0839] First, under a nitrogen atmosphere, charge the main chain G (75.00 g) into a polymerization vessel equipped with a stirrer and a reflux condenser and heat to 90 °C. Start Feed 1 (1.68 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 6.15 g of tripropylene glycol) and Feed 2 (75.00 g of vinyl acetate) 10 min after the start of Feed 1 and meter them into the stirred vessel at a variable feed rate for Feed 1 (0:00 h to 00:10 h: 2.61 g / h and 00:10 h to 06:10 h: 1.23 g / h) and a constant feed rate for Feed 2 (00:10 h to 06:10 h: 12.50 g / h). After the completion of Feed 1 and Feed 2, meter Feed 3 (0.53 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 1.94 g of tripropylene glycol) into the vessel at a constant feed rate at 90 °C over 0:56 h. After the complete addition of the feeds, stir the mixture at 90 °C for 1:00 h. Heat the polymerization mixture to 95 °C and apply a vacuum of 500 mbar to remove volatiles. The yield is 160 g of a polymer solution

[0840] Example 11 (invention 11)

[0841] First, under a nitrogen atmosphere, charge the main chain G (97.50 g) into a polymerization vessel equipped with a stirrer and a reflux condenser and heat to 90 °C. Start Feed 1 (0.60 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 6.92 g of propane-1,2-diol), Feed 2 (30.00 g of vinyl acetate), and Feed 3 (22.50 g of N-vinylpyrrolidone) simultaneously 10 min after the start of Feed 1 and meter them into the stirred vessel at a variable feed rate for Feed 1 (0:00 h to 00:10 h: 2.51 g / h and 00:10 h to 06:10 h: 3.75 g / h) and constant feed rates for Feed 2 (00:10 h to 06:10 h: 5.00 g / h) and Feed 3 (00:10 h to 06:10 h: 3.75 g / h). After the completion of Feed 1, Feed 2, and Feed 3, meter Feed 4 (0.38 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 4.44 g of propane-1,2-diol) into the vessel at a constant feed rate at 90 °C over 0:56 h. After the complete addition of the feeds, stir the mixture at 90 °C for 1:00 h. Heat the polymerization mixture to 95 °C and apply a vacuum of 500 mbar to remove volatiles. The yield is 162 g of a polymer solution.

[0842] Example 12 (invention 12)

[0843] Example 12a: Neopentyl glycol modified with 8 moles of caprolactone

[0844] In a 4-necked vessel equipped with a thermometer, a reflux condenser, a nitrogen inlet, a dropping funnel, and a stirrer, 104.1 g of neopentyl glycol and 1.0 g of tin(II) 2-ethylhexanoate were placed and heated to 140 °C. 913.0 g of ε-caprolactone was added over 15 minutes. The reaction mixture was heated to 160 °C to 205 °C and stirred at 160 °C under nitrogen for 4 hours. After cooling to room temperature, 971.0 g of a light yellow oil was obtained. The 1 1H-NMR in CDCl3 indicated a 99.0% conversion of caprolactone.

[0845] Example 12b: Neopentyl glycol modified with 8 moles of caprolactone and ethoxylated with 46 moles of ethylene oxide (main chain H)

[0846] In a 2 l autoclave, 356.1 g of neopentyl glycol modified with 8 moles of caprolactone (Example 12a) and 2.01 g of potassium tert-butoxide were placed and the mixture was heated to 80 °C. The vessel was purged with nitrogen three times and the mixture was heated to 140 °C. 709.2 g of ethylene oxide was added over 14 hours. To complete the reaction, the mixture was allowed to post-react at 140 °C for an additional 5 hours. The reaction mixture was stripped with nitrogen and the volatile compounds were removed in vacuo at 80 °C. 1.1 g of acetic acid was added. After filtration, 1060.0 g of a light brown solid was obtained. 1H-NMR in CDCl3 confirmed the expected structure.

[0847] Example 12c (graft polymer)

[0848] First, the main chain H (79.80 g) was charged into a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere and heated to 90 °C. Feed 1 (1.49 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 13.17 g of tripropylene glycol) and, 10 min after the start of Feed 1, Feed 2 (53.20 g of vinyl acetate) were started and metered into the stirred vessel at a variable feed rate for Feed 1 (0:00 h to 00:10 h: 4.89 g / h and 00:10 h to 06:10 h: 0.23 g / h) and a constant feed rate for Feed 2 (00:10 h to 06:10 h: 8.87 g / h). After the completion of Feed 1 and Feed 2, Feed 3 (0.34 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 2.99 g of tripropylene glycol) was metered in at a constant feed rate at 90 °C over 0:56 h. After the complete addition of the feeds, the mixture was stirred at 90 °C for 1:00 h. The polymerization mixture was heated to 95 °C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 150 g of a polymer solution

[0849] Example 13 (invention 13)

[0850] Example 13a: Neopentyl glycol modified with 8 moles of caprolactone and alkoxylated with a mixture of 40 moles of ethylene oxide and 4 moles of propylene oxide (main chain I)

[0851] In a 2 l autoclave, 300.0 g of neopentyl glycol modified with 8 moles of caprolactone (Example 12a) and 1.8 g of potassium tert-butoxide were placed, and the mixture was heated to 80 °C. The vessel was purged three times with nitrogen and the mixture was heated to 140 °C. A mixture of 519.6 g of ethylene oxide and 68.5 g of propylene oxide was added within 14 h. To complete the reaction, the mixture was allowed to post-react for an additional 5 h at 140 °C. The reaction mixture was stripped with nitrogen and the volatile compounds were removed in vacuo at 80 °C. 0.9 g of acetic acid was added. After filtration, 880.0 g of a light brown oil was obtained. 1H-NMR in CDCl3 confirmed the expected structure.

[0852] Example 13b (graft polymer)

[0853] First, the main chain I (78.00 g) was charged into a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere and heated to 90 °C. Feed 1 (1.35 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 11.88 g of tripropylene glycol) and Feed 2 (42.00 g of vinyl acetate) starting 10 min after Feed 1 were started and metered into the stirred vessel at a variable feed rate of Feed 1 (0:00 h to 00:10 h: 4.41 g / h and 00:10 h to 06:10 h: 0.23 g / h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 7.09 g / h). After Feed 1 and Feed 2 were completed, Feed 3 (0.31 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 2.70 g of tripropylene glycol) was metered in at a constant feed rate at 90 °C within 0:56 h. After the complete addition of the feeds, the mixture was stirred at 90 °C for 1:00 h. The polymerization mixture was heated to 95 °C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 136 g of a polymer solution

[0854] Example 14 (invention 14)

[0855] First, under a nitrogen atmosphere, the main chain I (97.50 g) was charged into a polymerization vessel equipped with a stirrer and a reflux condenser and heated to 90 °C. Feed 1 (1.22 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 12.33 g of propane-1,2-diol), Feed 2 (45.00 g of vinyl acetate) starting 10 min after Feed 1, and Feed 3 (7.50 g of N-vinylpyrrolidone) were started simultaneously and metered into the stirred vessel at a variable feed rate for Feed 1 (0:00 h to 00:10 h: 4.49 g / h and 00:10 h to 06:10 h: 1.25 g / h) and at a constant feed rate for Feed 2 (00:10 h to 06:10 h: 7.50 g / h) and Feed 3 (00:10 h to 06:10 h: 1.25 g / h). After the completion of Feed 1, Feed 2, and Feed 3, Feed 4 (0.38 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 3.80 g of propane-1,2-diol) was metered in at a constant feed rate at 90 °C over 0:56 h. After the complete addition of the feeds, the mixture was stirred at 90 °C for 1:00 h. The polymerization mixture was heated to 95 °C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 165 g of a polymer solution.

[0856] Example 15 (invention 15)

[0857] First, under a nitrogen atmosphere, the main chain I (97.50 g) was charged into a polymerization vessel equipped with a stirrer and a reflux condenser and heated to 90 °C. Feed 1 (1.22 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 12.33 g of propane-1,2-diol), Feed 2 (37.50 g of vinyl acetate) starting 10 min after Feed 1, and Feed 3 (15.00 g of N-vinylpyrrolidone) were started simultaneously and metered into the stirred vessel at a variable feed rate for Feed 1 (0:00 h to 00:10 h: 4.49 g / h and 00:10 h to 06:10 h: 2.12 g / h) and at a constant feed rate for Feed 2 (00:10 h to 06:10 h: 6.25 g / h) and Feed 3 (00:10 h to 06:10 h: 2.50 g / h). After the completion of Feed 1, Feed 2, and Feed 3, Feed 4 (0.38 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 3.80 g of propane-1,2-diol) was metered in at a constant feed rate at 90 °C over 0:56 h. After the complete addition of the feeds, the mixture was stirred at 90 °C for 1:00 h. The polymerization mixture was heated to 95 °C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 167 g of a polymer solution.

[0858] Example 16 (invention 16)

[0859] First, 97.50 g of main chain I was charged into a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere and heated to 90 °C. Feed 1 (1.22 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 12.33 g of propane-1,2-diol), Feed 2 (30.00 g of vinyl acetate) starting 10 min after Feed 1, and Feed 3 (22.50 g of N-vinylpyrrolidone) were started simultaneously and metered into the stirred vessel at a variable feed rate for Feed 1 (0:00 h to 00:10 h: 4.49 g / h and 00:10 h to 06:10 h: 2.12 g / h) and constant feed rates for Feed 2 (00:10 h to 06:10 h: 5.00 g / h) and Feed 3 (00:10 h to 06:10 h: 3.75 g / h). After completion of Feed 1, Feed 2, and Feed 3, Feed 4 (0.38 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 3.80 g of propane-1,2-diol) was metered in at a constant feed rate at 90 °C over 0:56 h. After complete addition of the feeds, the mixture was stirred at 90 °C for 1:00 h. The polymerization mixture was heated to 95 °C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 165 g of a polymer solution.

[0860] Example 17 (invention 17)

[0861] Example 17a: Neopentyl glycol modified with 2 moles of caprolactone

[0862] In a 4-necked vessel equipped with a thermometer, a reflux condenser, a nitrogen inlet, a dropping funnel, and a stirrer, 156.2 g of neopentyl glycol and 0.5 g of tin(II) ethylhexanoate were placed and heated to 140 °C. 342.4 g of ε-caprolactone was added over 15 minutes. The reaction mixture was heated to 160 °C and stirred under nitrogen at 160 °C for 2 hours. After cooling to room temperature, 477.0 g of a light yellow oil was obtained. The 1 1H-NMR in CDCl3 indicated a 99.0% conversion of caprolactone.

[0863] Example 17b: Neopentyl glycol modified with 2 moles of caprolactone and ethoxylated with 40 moles of ethylene oxide (main chain J)

[0864] In a 2 l autoclave, 149.6 g of neopentyl glycol modified with 2 moles of caprolactone (Example 17a) and 1.9 g of potassium tert-butoxide were placed, and the mixture was heated to 80 °C. The vessel was purged with nitrogen three times and the mixture was heated to 140 °C. 792.0 g of ethylene oxide were added within 14 hours. To complete the reaction, the mixture was allowed to post-react at 140 °C for an additional 5 hours. The reaction mixture was stripped with nitrogen and the volatile compounds were removed in vacuo at 80 °C. 1.0 g of acetic acid was added. After filtration, 940.0 g of a light brown oil was obtained. 1H-NMR in CDCl3 confirmed the expected structure.

[0865] Example 17c (graft polymer)

[0866] First, the main chain J (97.50 g) was charged into a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere and heated to 90 °C. Feed 1 (1.68 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 6.15 g of tripropylene glycol), Feed 2 (37.50 g of vinyl acetate) starting 10 min after Feed 1, and Feed 3 (15.00 g of vinyl laurate) were started simultaneously and metered into the stirred vessel at a variable feed rate for Feed 1 (0:00 h to 00:10 h: 2.61 g / h and 00:10 h to 06:10 h: 1.23 g / h) and constant feed rates for Feed 2 (00:10 h to 06:10 h: 6.25 g / h) and Feed 3 (00:10 h to 06:10 h: 2.50 g / h). After the completion of Feed 1, Feed 2, and Feed 3, Feed 4 (0.54 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 1.96 g of tripropylene glycol) was metered in at a constant feed rate at 90 °C within 0:56 h. After the complete addition of the feeds, the mixture was stirred at 90 °C for 1:00 h. The polymerization mixture was heated to 95 °C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 159 g of a polymer solution.

[0867] Example 18 (invention 18) (hydrolysis)

[0868] First, Example 8b (110.00 g) was charged into a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere and heated to 80 °C. Water (49.86 g) was added, and Feed 1 (an aqueous sodium hydroxide solution, 50%, 11.50 g) was started at a constant feed rate within 1:00 h. After the addition was completed, the mixture was stirred at 80 °C for 1 h to obtain 250 g of a polymer solution.

[0869] Example 19 (invention 19)

[0870] Example 19a: Polyethylene glycol (molecular weight 400 g / mol) modified with 6 moles of caprolactone and 70 moles of ethylene oxide (main chain B):

[0871] In a 2 l autoclave, 150 g of polyethylene glycol (molecular weight 400 g / mol) and 2.7 g of potassium tert-butoxide were placed, and the mixture was heated to 80 °C. The vessel was purged with nitrogen three times and the mixture was heated to 140 °C. A mixture of 977.5 g of ethylene oxide and 217.1 g of caprolactone was added over 15 h. To complete the reaction, the mixture was allowed to post-react at 140 °C for an additional 5 h. The reaction mixture was stripped with nitrogen and the volatile compounds were removed in vacuo at 80 °C. After filtration, 1340.0 g of a light brown solid was obtained. 1H-NMR in CDCl3 confirmed the expected structure.

[0872] Example 19b (graft polymer)

[0873] First, the main chain B (480.0 g) was charged into a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere and heated to 90 °C. Feed 1 (2.97 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 26.1 g of propane-1,2-diol) and Feed 2 (258.5 g of vinyl acetate) starting 10 min after Feed 1 were started simultaneously and metered into the stirred vessel at a variable feed rate for Feed 1 (0:00 h to 00:10 h: 9.70 g / h and 00:10 h to 06:10 h: 4.58 g / h) and a constant feed rate for Feed 2 (00:10 h to 06:10 h: 43.08 g / h). After Feed 1 and Feed 2 were completed, Feed 3 (1.88 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 16.6 g of propane-1,2-diol) was metered in at a constant feed rate at 90 °C over 0:56 h. After complete addition of the feeds, the mixture was stirred at 90 °C for 1 h. The polymerization mixture was heated to 95 °C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 781 g of a polymer solution.

[0874] Example 20 (invention 20)

[0875] Example 20a: Polyethylene glycol (molecular weight 400 g / mol) modified with 6 moles of caprolactone and 70 moles of ethylene oxide (main chain K):

[0876] In a 2 L autoclave, 150 g of polyethylene glycol (molecular weight 400 g / mol) and 2.7 g of potassium tert-butoxide were placed, and the mixture was heated to 80 °C. The vessel was purged with nitrogen three times and the mixture was heated to 140 °C. A mixture of 977.5 g of ethylene oxide and 217.1 g of caprolactone was added over 15 h. To complete the reaction, the mixture was allowed to post-react at 140 °C for an additional 5 h. The reaction mixture was stripped with nitrogen and the volatile compounds were removed in vacuo at 80 °C. After filtration, 1340.0 g of a light brown solid was obtained. 1H-NMR in CDCl3 confirmed the expected structure.

[0877] Example 20b (graft polymer)

[0878] First, the main chain K (350.0 g) was charged into a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere and heated to 90 °C. Feed 1 (4.02 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 33.0 g of propane-1,2-diol) and Feed 2 (650.0 g of vinyl acetate) starting 10 min after Feed 1 were started simultaneously and metered into the stirred vessel at a variable feed rate of Feed 1 (0:00 h to 00:10 h: 12.4 g / h and 00:10 h to 06:10 h: 5.83 g / h) and a constant feed rate of Feed 2 (00:10 h to 06:10 h: 108.3 g / h). After Feed 1 and Feed 2 were completed, Feed 3 (2.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 21.0 g of propane-1,2-diol) was metered in at a constant feed rate at 90 °C over 0:56 h. After complete addition of the feeds, the mixture was stirred at 90 °C for 1 h. The polymerization mixture was heated to 95 °C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 1059 g of a polymer solution.

[0879] Example 21 (invention 21 - graft polymer)

[0880] First, under a nitrogen atmosphere, the main chain K (550.0 g) was charged into a polymerization vessel equipped with a stirrer and a reflux condenser and heated to 90 °C. Feed 1 (3.40 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 30.0 g of propane-1,2-diol) and Feed 2 (296.2 g of vinyl acetate) starting 10 min after the start of Feed 1 were simultaneously started and metered into the stirred vessel at a variable feed rate for Feed 1 (0:00 h to 00:10 h: 11.1 g / h and 00:10 h to 06:10 h: 5.25 g / h) and a constant feed rate for Feed 2 (00:10 h to 06:10 h: 49.4 g / h). After the completion of Feed 1 and Feed 2, Feed 3 (2.55 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 21.0 g of propane-1,2-diol) was metered in at a constant feed rate at 90 °C over 0:56 h. After the complete addition of the feeds, the mixture was stirred at 90 °C for 1 h. The polymerization mixture was heated to 95 °C and a vacuum of 500 mbar was applied to remove volatiles. The yield was 899 g of a polymer solution.

[0881] Synthesis of Comparative Graft Polymer 1: (Based on unpublished patent application PCT / EP2022 / 065983, now published as WO 2022 / 263354)

[0882] Comparative Graft Polymer 1 based on a PEG ester main chain was synthesized via the following Step 1.3:

[0883] Step 1: Oxidation of PAG

[0884] A polyalkylene glycol (PAG) having two primary OH end groups (referred to as "diol") was oxidized to a mixture comprising at least a polyalkylene glycol having two COOH end groups (referred to as "diacid"), a polyalkylene glycol having one primary OH and one COOH end group (referred to as "monoacid"), and optionally, also a polyalkylene glycol having two primary OH end groups. The mixture was prepared as follows.

[0885] Platinum / charcoal (5.0 wt.-% Pt / C, water content: 59.7 wt.-%, 283 g, 29.2 mmol Pt) was suspended in a mixture of a polyalkylene oxide having two primary OH end groups and water (details see Table 1), heated to 52 °C and stirred at 800 rpm. Oxygen was passed through the stirred mixture (20 nL / h) via a glass tube equipped with a fritted disc and the temperature was allowed to rise to 60 °C. The oxygen dosage and temperature were maintained for the period of time mentioned in Table 1, then the oxygen dosage was stopped and the mixture was allowed to cool to room temperature. The solid was separated from the liquid phase by filtration and the filter cake was washed with 500 mL of warm water. The wash water was mixed with the filtrate. Water was removed from the liquid mixture by distillation through a wiped-film evaporator (total height: 87.2 cm, diameter: 3.54 cm, wiped-film height: 43 cm, feed: 4.0 mL / min, 44 °C, 1.8 kPa absolute, 600 rpm).

[0886] Polymer backbone - Table 1 - Oxidation of PEG

[0887]

[0888] #1 EO = polyethylene oxide

[0889] #2 Calculation based on the acid value of the reaction solution

[0890] Step 2: Esterification

[0891] A mixture of the oxidized polyalkylene oxide obtained by oxidation of the diol (see Table 1) (see Table 2) and an esterification catalyst (see Table 2) was mixed and heated under vacuum at a pressure of 1 kPa absolute at a temperature of 135 °C for the period of time mentioned in Table 2.

[0892] Table 2 - Esterification to PEG-ester

[0893]

[0894] Notes on polymer backbone - Table 2:

[0895] #1 Catalyst = zinc octanoate

[0896] #2 The K-value measures the relative viscosity of a dilute polymer solution and is a relative measure of the average molecular weight. When the average molecular weight of a particular polymer increases, the K-value also tends to increase. The K-value was determined at 23 °C in a polymer concentration of 3% by weight of NaCl solution and 1% polymer according to the method of H. Fikentscher in "Cellulosechemie [Cellulose Chemistry]", 1932, 13, 58.

[0897] Step 3: Comparison of the synthesis of graft polymer 1

[0898] The polymer backbone B1 (350.0 g) was metered into a vessel equipped with a stainless steel anchor stirrer (and 2 other necks) and heated to 95 °C. A 14 wt% solution of 1.00 g of tert-butyl peroxy-2-ethylhexanoate in tripropylene glycol was added within 1 min. Thereafter, the dosing of vinyl acetate (350.0 g) was started and continued at a constant feed rate for more than 7.5 h. At the same time, within 8.5 h, the initiator solution (50.0 g) of tert-butyl peroxy-2-ethylhexanoate as a 14 wt% solution in tripropylene glycol was metered in at a constant feed rate. To complete the reaction, the mixture was stirred for an additional 180 minutes. Finally, the volatile components were stripped with nitrogen at 120 °C at a feed rate of 6 L N2 / h for 90 minutes.

[0899] Synthesis procedures of comparative polymers - Comparative Examples 2 - 5

[0900] The procedures followed the method descriptions disclosed to produce polymers known and used in the prior art literature.

[0901] Comparative Example 2: Graft polymerization of vinyl acetate (40 wt%) on PEG (Mn 6000 g / mol; 60 wt%)

[0902] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with 660 g of PEG (Mn 6000 g / mol) under a nitrogen atmosphere 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 metered into the stirred vessel at 90 °C over 6:10 h. 5.56 wt.-% of Feed 1 was metered in during the first 10 min and the remainder was metered in at a constant feed rate for 6:00 h. Ten minutes after the start of Feed 1, Feed 2 (440 g of vinyl acetate) was started and metered in at a constant feed rate and at 90 °C over 6:00 h. After the completion of Feeds 1 and 2, the temperature was raised 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 metered in at a constant feed rate at 95 °C over 56 min. After the complete addition of the feeds, the mixture was stirred at 95 °C for one hour. The residual amount of monomer was removed by vacuum distillation at 95 °C and 500 mbar for 1 h.

[0903] Comparative Example 3: Graft polymerization of vinyl acetate (30 wt%) on PEG (Mn 6000 g / mol; 70 wt%)

[0904] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with 700 g of PEG (Mn 6000 g / mol) under a nitrogen atmosphere and melted at 90 °C. Feed 1, which contained 12.24 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 50.30 g of tripropylene glycol, was metered into the stirred vessel at 90 °C over 6:10 h. 5.56 wt.-% of Feed 1 was metered in during the first 10 min and the remainder was metered in at a constant feed rate for 6:00 h. Ten minutes after the start of Feed 1, Feed 2 (300 g of vinyl acetate) was started and metered in at a constant feed rate and at 90 °C over 6:00 h. After the completion of Feeds 1 and 2, the temperature was raised to 95 °C, and Feed 3, which consisted of 4.80 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 19.70 g of tripropylene glycol, was metered in at a constant feed rate at 95 °C over 56 min. After the complete addition of the feeds, the mixture was stirred at 95 °C for one hour. The residual amount of monomer was removed by vacuum distillation at 95 °C and 500 mbar for 1 h.

[0905] Comparative Example 4: Graft polymerization of vinyl acetate (40 wt%) onto PEG (Mn 4000 g / mol; 60 wt%)

[0906] A polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with 600 g of PEG (Mn 4000 g / mol) under a nitrogen atmosphere and melted at 90 °C. Feed 1, which contained 3.57 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 29.90 g of tripropylene glycol, was metered into the stirred vessel at 90 °C over 6:10 h. 5.56 wt.-% of Feed 1 was metered in during the first 10 min and the remainder was metered in at a constant feed rate for 6:00 h. Ten minutes after the start of Feed 1, Feed 2 (400 g of vinyl acetate) was started and metered in at a constant feed rate and at 90 °C over 6:00 h. After the completion of Feeds 1 and 2, the temperature was raised to 95 °C, and Feed 3, which consisted of 4.90 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 41.00 g of tripropylene glycol, was metered in at a constant feed rate at 95 °C over 56 min. After the complete addition of the feeds, the mixture was stirred at 95 °C for one hour. The residual amount of monomer was removed by vacuum distillation at 95 °C and 500 mbar for 1 h.

[0907] Comparative Example 5: Graft polymerization of vinyl acetate (60 wt%) onto PEG (Mn 6000 g / mol; 40 wt%)

[0908] The polymerization vessel equipped with a stirrer and a reflux condenser was initially charged with 400 g of PEG (Mn 6000 g / mol) under a nitrogen atmosphere and melted at 90 °C. Feed 1, which contained 4.8 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 23.6 g of tripropylene glycol, was metered into the stirred vessel at 90 °C over 6:10 h. 5.56 wt.-% of Feed 1 was metered in during the first 10 min and the remainder was metered in at a constant feed rate over 6:00 h. 10 minutes after the start of Feed 1, Feed 2 (600 g of vinyl acetate) was started and metered in at a constant feed rate over 6:00 h and at 90 °C. After the completion of Feeds 1 and 2, the temperature was raised to 95 °C, and Feed 3, which consisted of 3.16 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 15.70 g of tripropylene glycol, was metered in at a constant feed rate over 56 min at 95 °C. After the complete addition of the feeds, the mixture was stirred at 95 °C for one hour. The residual amount of monomer was removed by vacuum distillation at 95 °C and 500 mbar for 1 h.

[0909] Table - Comparative graft polymer Examples 2 to 5

[0910]

[0911] Note: VAc: Vinyl acetate

[0912] Polymer biodegradability

[0913] The biodegradation of the polymers in wastewater was tested in triplicate using OECD 301F manometric respirometry. 30 mg / mL of the test substance was inoculated into wastewater extracted from the Mannheim wastewater treatment plant and incubated in a closed flask at 25 °C for 28 days. During this time, the oxygen consumption was measured as the change in pressure inside the flask using an OxiTop C (WTW). The CO2 evolved was absorbed using a NaOH solution. After blank correction, the amount of oxygen consumed by the microbial population during the biodegradation of the test substance was expressed as a percentage of the ThOD (theoretical oxygen demand).

[0914] The biodegradation data of the comparative polymers and the polymers of the present invention on the 28th day of the OECD 301F test are summarized in the table before the synthesis description.

[0915] As shown in the table, the graft polymers of the present invention typically show a higher percentage of biodegradation on the 28th day of the OECD 301F test.

[0916] Stability of the graft polymer 5 of the present invention (Present Invention 5) relative to comparative graft polymer 1

[0917] An aqueous solution of the graft polymer of the present invention 5 (invention 5) and the comparative polymer 1 (9 wt%) was prepared and the mixture was stored at 54 °C for two weeks.

[0918] During storage of the comparative graft polymer 1, a brown precipitate formed. The recorded 1H NMR (298 K, D2O, 400 MHz) spectra of the precipitate and the solution showed no difference. Comparison of the 1H NMR spectra of fresh and stored samples of the comparative graft polymer showed 1 significant rearrangements in the regions of 1H NMR shifts at 4.0 to 4.35 ppm (typical for PEG-ester bonds) and 1.8 to 2.2 ppm (typical for bound / unbound acetate), as 1 shown in 1 Comparison of the 1H NMR spectra (298 K, D2O, 400 MHz) of fresh and stored samples of the graft polymer of the present invention (invention 5) showed no significant rearrangements in the spectra as Figure 2 shown in.

[0919] These results clearly show better hydrolytic instability of the polymers from the present invention. 1 These results clearly show better hydrolytic instability of the polymers from the present invention. Table 3: Greasy soil shown in the spectra shown in.

[0920] These results clearly show better hydrolytic instability of the polymers from the present invention.

[0921] Method for evaluating the foam persistence of a manual dishware composition

[0922] The purpose of the Suds Mileage Index test is to compare the evolution of the foam volume over time generated by different test formulations at a specified water hardness, solution temperature, and formulation concentration, while under the influence of regular soil injection. The data is compared to a reference composition and expressed as a Suds Mileage Index (the reference composition has a Suds Mileage Index of 100). The steps of the method are as follows:

[0923] 1) Depending on the target composition concentration (0.12 wt%), a defined amount of the test composition is dispensed through a plastic pipette at a flow rate of 0.67 mL / second at a height of 37 cm above the bottom surface of a sink (dimensions: 300 mm diameter and 288 mm height) into a water stream (water hardness: 15 gpg, water temperature: 35 °C) that fills the sink to 4 L at a constant pressure of 4 bar.

[0924] 2) Immediately after filling is complete, the initial foam volume generated is recorded (measured as the average foam height × sink surface area and expressed in cm 3 ).

[0925] 3) A fixed amount (6 mL) of soil is immediately injected into the middle of the sink.

[0926] 4) The resulting solution is mixed by rotating a metal blade (10 cm × 5 cm) at the gas-liquid interface in the middle of the water tank at a 45-degree angle at 85 RPM for 20 revolutions.

[0927] 5) Immediately after the blade rotation ends, another measurement of the total foam volume is recorded.

[0928] 6) Repeat steps 3 - 5 until the measured total foam volume reaches a minimum level of 400 cm 3 The amount of added soil required to reach the 400 cm 3 level is considered the foam persistence of the test composition.

[0929] 7) Each test composition is tested 4 times according to the test conditions (i.e., water temperature, composition concentration, water hardness, soil type).

[0930] 8) The average foam persistence is calculated as the average of 4 replicates for each sample.

[0931] 9) The foam persistence index is calculated by comparing the average persistence of the test composition samples relative to the reference composition samples. The calculation is as follows:

[0932]

[0933] The soil composition is produced by standard mixing of the components described in Table 3.

[0934] Ingredients

[0935] Weight % Crisco oil Crisco shortening 12.730 Lard 27.752 Refined edible beef tallow 7.638 Oleic acid, 90% (technical grade) 51.684 Palmitic acid, 99+% 0.139 Stearic acid, 99+% 0.036 Code 0.021

[0936] Method for Evaluating the Whiteness Benefit of Polymers in Laundry Detergents

[0937] Whiteness maintenance, also known as whiteness retention, is the ability of a detergent to keep white items free from whiteness loss when washing in the presence of soil. When soil is removed from dirty clothes and suspended in the wash water, white clothes may become dirty / smudged over time, and then this soil may redeposit onto the clothes, making the clothes less white each time they are washed.

[0938] The whiteness benefit of the polymers of the present disclosure is evaluated using an automatic soil removal tester with 10 jars for testing laundry formulations.

[0939] The SBL2004 test soil strip supplied by WFK Testgewebe GmbH is used to simulate the user soil level (a mixture of human soil, food, dirt, etc.). On average, each SBL2004 strip is loaded with 8 g of soil. The SBL2004 test soil strip is cut into 5 x 5 cm squares for use in the test.

[0940] The following white fabric samples in Table 4 purchased from WFK Testgewebe GmbH are used as whiteness tracers. Before the washing test, the L, a, b values of all whiteness tracers are measured using a Konica Minolta CM-3610D spectrophotometer.

[0941] Table 4

[0942] Fiber content % fiber content Fabric construction Dimensions WFK code CK Cotton Weft knitted fabric 100 (5x5cm) 19502_5x5_stamped PC Polyester / cotton Woven 65 / 35 (5x5cm) 19503_5x5_stamped PE Polyester Weft knitted fabric 100 (5x5cm) 19508_5x5_stamped PS Weft knitted fabric <![CDATA[Polyester / Spandex TM > 95 / 5 (5x5cm) 19507_5x5_stamped The polymer of the present invention

[0943] Additional ballast (background fabric samples) is also used to simulate the fabric load and provide mechanical energy during actual laundering. The ballast load consists of cotton and polycotton knitted fabric samples in 5 x 5 cm sizes.

[0944] Four washing cycles are required to complete the test:

[0945] Cycle 1: The desired amount of detergent is completely dissolved by mixing with 1 L of water (at the defined hardness) in each detergent meter port. Under the defined conditions, 60 g of fabric (including whiteness tracers) (4 types, each with 4 replicates), 21 pieces of 5 x 5 cm SBL2004, and ballast are washed and rinsed in the detergent meter tank.

[0946] In the test of the water-soluble unit dose composition, the washing concentration is 2000 ppm. An additional 47 ppm PVOH film is also added to the detergent meter tank. The washing temperature is 30 °C and the water hardness is 20 gpg.

[0947] Cycle 2: Then, after the process of Cycle 1, the whiteness tracers and ballast from each tank are washed and rinsed again together with a new set of SBL2004 (5 x 5 cm, 21 pieces). All other conditions remain the same as in Cycle 1.

[0948] Cycle 3: Then, after the process of Cycle 1, the whiteness tracers and ballast from each tank are washed and rinsed again together with a new set of SBL2004 (5 x 5 cm, 21 pieces). All other conditions remain the same as in Cycle 1.

[0949] Cycle 4: Then, after the process of Cycle 1, the whiteness tracers and ballasts from each port are washed and rinsed again together with a new set of SBL2004 (5x5 cm, 21 pieces). All other conditions remain the same as in Cycle 1.

[0950] After Cycle 4, all the whiteness tracers and ballasts are tumble dried between 60 °C - 65 °C until dry, and then the tracers are measured again using a Konica Minolta CM - 3610D spectrophotometer. The change in whiteness index (ΔWI(CIE)) is calculated based on the L, a, b measurement values before and after washing.

[0951] ΔWI(CIE) = WI(CIE) (after washing) - WI(CIE) (before washing).

[0952] Method for evaluating the stain removal benefit of polymers in laundry detergents

[0953] The cleaning benefit of the polymer is evaluated using a tergotometer. Some example test stains applicable to this test are:

[0954] Standard grass, ex CFT

[0955] Standard clay, ex CFT

[0956] ASTM dust sebum, ex CFT

[0957] Highly discriminative sebum on polyester cotton, ex CFT

[0958] Burnt bacon on knitted cotton (prepared using burnt bacon from Equest Corporation)

[0959] Dyed bacon on knitted cotton (prepared using dyed bacon from Equest Corporation)

[0960] For the laundry stain removal test before and after washing, an image analysis system is used to analyze the stains.

[0961] The SBL2004 test soil strips supplied by WFK Testgewebe GmbH are used to simulate the user soil level (a mixture of human soil, food, dirt, etc.). On average, each SBL2004 strip is loaded with 8 g of soil. The SBL2004 test soil strips are cut into 5x5 cm squares for use in the test.

[0962] Additional ballasts (background fabric samples) are also used to simulate the fabric load and provide mechanical energy during actual laundering. The ballast load consists of knitted cotton samples in 5x5 cm size. Four washing cycles are carried out:

[0963] The desired amount of detergent is completely dissolved by mixing it with 1 L of water (at the defined hardness) in each dishwasher port. Under the defined conditions, 60 grams of fabric, stains (2 internal replicates of each stain per tank), 13 pieces of 5 x 5 cm SBL2004, and ballast are washed and rinsed in the dishwasher tank. In the test of water-soluble unit-dose compositions, the washing concentration is 2000 ppm. An additional 47 ppm PVOH film is also added to the dishwasher tank. The washing temperature is 30 °C and the water hardness is 7 gpg. The test has four external replicates.

[0964] All stains are tumble-dried between 60 °C and 65 °C until dry, and then for the laundry stain removal test, the stains are measured again using an image analysis system.

[0965] The stain removal index (SRI) is automatically calculated from the L, a, b values using the formula shown below. The higher the SRI, the better the stain removal.

[0966] SRI = 100 * ((ΔE b - ΔE a ) / ΔE b )

[0967] ΔE b = √((L c - L b ) 2 + (a c - a b ) 2 + (b c - b b ) 2 )

[0968] ΔE a = √((L c - L a ) 2 + (a c - a a ) 2 + (b c - b a ) 2 )

[0969] The subscript ‘b’ indicates the data of the st...

Claims

1. A graft polymer, characterized in that: (A) 20% to 95%, preferably 30% to 90%, more preferably 40% to 85%, most preferably 50% to 80% of the polymer main chain as the graft matrix, The polymer main chain contains at least one subunit (a1) and at least one subunit (a2), where (a1) is a unit containing a moiety - preferably consisting essentially of - derived from at least one alkylene oxide monomer and / or at least one polyalkylene oxide-polymer having two hydroxyl end groups, and the alkylene oxide monomer is selected from the group of C2- to C10-alkylene oxides, preferably C2 to C5-alkylene oxides, (a2) is a unit containing a moiety - preferably consisting of - derived from at least one lactone and / or at least one hydroxy acid, and this subunit (a2) is a moiety derived from a single lactone and / or hydroxy acid or an oligomeric or polymeric unit composed of at least one type of lactone and / or at least one type of hydroxy acid, Where preferably the at least one lactone and / or hydroxy acid is selected from group i) and / or ii), where i) Lactones, i.e., cyclic esters, starting with α-lactones (three ring atoms), followed by β-lactones (four ring atoms), γ-lactones (five ring atoms), etc.; such lactones are preferably β-propiolactone, g-butyrolactone, δ-valerolactone, g-valerolactone, e-caprolactone, d-decalactone, g-decalactone, e-decalactone; preferably caprolactone; And ii) Hydroxy acids, which can be derived by hydrolysis from any lactone, especially from any lactone within the previous group i), especially α-, β- or γ-hydroxy acids derived by hydrolysis from the corresponding lactone, as well as lactic acid, glycolic acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 12-hydroxystearic acid, citric acid; Preferably lactic acid or caprolactone, more preferably caprolactone, Where the polymer main chain a) is obtained by: (A1) Copolymerization of at least one subunit (a1) and at least one subunit (a2), where optionally, at least one oligomer or polymer made from at least one subunit (a1) or at least one subunit (a2) can also be used in the copolymerization of the at least one subunit (a1) and the at least one subunit (a2); (A2) First oligomerize / polymerize the subunit (a2), and then polymerize the product with the subunit (a1); (A3) First oligomerize / polymerize the subunit (a1), and then copolymerize the product with the subunit (a2); or (A4) First, provide an oligomeric or polymeric subunit (a1) with a capping group on one side, preferably etherified with an alcohol, more preferably a short-chain alcohol C1 to C4. As a starting block, it then reacts with at least one subunit (a2) and optionally at least one subunit (a1), where the subunit (a1) can be different from those in the starting block or can be arranged in a different order compared to those in the starting block, to attach a new block containing a portion of the subunits for (co)polymerization to the uncapped side of the starting block, thereby obtaining a diblock structure of [capping group]-[subunit (a1)]-[subunit (a2)], or [capping group]-[subunit (a1)]-[random-{subunit (a2)-subunit (a1)}]; where in the case where more than one subunit (a1) and / or more than one subunit (a2) are already present in the oligomer or polymer employed, those subunits can be arranged in any order within such an oligomer or polymer employed, and where in the case where more than one subunit (a1) and / or more than one subunit (a2) are used for polymerization, those subunits (and optionally the oligomer / polymer, if employed) can be arranged in any order within the resulting main chain; and where in the cases of (A1), (A2), and (A3), the use of a starting molecule is optional; or b) selected from: (A1) A main chain composed of monomers, oligomeric, and / or polymeric (a1)-subunits and monomers, oligomeric, and / or polymeric (a2)-subunits in a random arrangement order, where there are more than one subunit (a1) and / or more than one subunit (a2); (A2) A main chain composed of an oligomeric subunit or a polymeric subunit (a2) as an internal block and two outer blocks of oligomeric and / or polymeric (a1)-subunits, which is defined as "-[block of (a1)]-[block of (a2)]-[block of (a1)]-", and may also contain higher-order block polymers, such as pentablock, heptablock, and nonablock, etc., where additional blocks of (a1) and (a2) are connected at the outer part of the triblock structure, such as the pentablock "[block of (a1)]-[block of (a2)]-[block of (a1)]-[block of (a2)]-[block of (a1)]-[block of (a2)]-[block of (a1)]", etc.; (A3) A main chain composed of an internal block of oligomeric and / or polymeric (a1)-subunits and two outer blocks of an oligomeric or polymeric subunit (a2), which is at least in the form of a triblock polymer defined as "-[block of (a2)]-[block of (a1)]-[block of (a2)]-"; and (A4) A main chain composed of: A first block having (i) A capping group at one end - such a capping group is attached to the C1 to C18, preferably C1 - C4 - alkyl of the first block via an ether functional group; and (ii) An oligomeric or polymeric subunit (a1); and a second block attached to the first block at the opposite end of the first block (opposite with respect to the capping group on the first block) via an ether or ester functional group, the second block being composed of at least one subunit (a2) and optionally at least one subunit (a1), where the optional subunit (a1) in the second block may be different from that / those in the first block or may be arranged in an order different from those in the first block, and the order of these subunits (A1) and (a2) may also be in any order, including a random structure, Such a diblock structure has the following as an idealized structure in the case where only the subunit (a2) is used for the second block: [capping group]-[subunit (a1)]-[subunit (a2)] or has the following as an idealized structure in the case where the subunits (a1) and (a2) are used for the second block: [capping group]-[subunit (a1)]-[random-{subunit (a2)-subunit (a1)}]; and where in the case of (A1), (A2) and (A3), the use of starting molecules is optional; and (B) 5% to 80%, preferably 10% to 70%, more preferably 15% to 60%, most preferably 20% to 50% of polymer side chains (B) grafted onto the polymer backbone (A), where the polymer side chains (B) are obtainable by the (co)polymerization of at least one vinyl ester monomer (B1), optionally a nitrogen-containing monomer (B2) and optionally further monomers (B3) and optionally further monomers, where all percentages are by weight relative to the total weight of the graft polymer.

2. The graft polymer according to claim 1, wherein At least two different alkylene oxides are used for preparing the backbone / present in the backbone.

3. The graft polymer according to claims 1 to 2, wherein These monomers are: (B1) at least one vinyl ester selected from vinyl acetate, vinyl propionate and / or vinyl laurate and any further vinyl esters known to the person skilled in the art, such as vinyl valerate, vinyl pivalate, vinyl neodecanoate, vinyl decanoate and / or vinyl benzoate; optionally (B2) At least one nitrogen-containing monomer selected from the group consisting of: vinyl lactams, vinyl imidazoles, 1-vinyltriazoles, 4-vinylpyridines, 4-vinylpyridine-N-oxides, 2-vinylpyridines, 1-vinyl oxazolidinones, N-vinylformamides, N-vinylacetamides, N-vinyl-N-methylacetamides, and acrylamides such as acrylamide, methacrylamide, N-alkyl-substituted acrylamides, N,N'-dialkyl(meth)acrylamides; mono- and dialkylamino-alkyl-(meth)acrylates, preferably vinyl lactam-monomers and / or vinyl imidazole-monomers, more preferably the vinyl lactam is selected from N-vinyl lactams such as N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, even more preferably N-vinylpyrrolidone, N-vinylcaprolactam, and most preferably N-vinylpyrrolidone, and the vinyl imidazole is preferably N-vinylimidazole, 2-methyl-1-imidazole, more preferably N-vinylimidazole; Optionally (B3) At least one additional monomer such as any one or more of 1-vinyl oxazolidinone and other vinyl oxazolidinones, 4-vinylpyridine-N-oxide, N-vinylformamide and its amines - if hydrolyzed after polymerization, N-vinylacetamide, N-vinyl-N-methylacetamide, alkyl esters of (meth)acrylic acid; and Optionally At least one additional monomer different from the previous ones, such other monomer being present in an amount of less than 2% of the total amount of monomers used to obtain the polymer side chain (B), and preferably only present as an impurity and not intentionally added for polymerization.

4. The graft polymer according to any one of claims 1 to 3, wherein, The amount of the following items - If (B2) is present - (B) is 10% to 60%, preferably up to 50%, more preferably up to 40% and preferably 20%; Based on the total weight of the graft polymer in weight percentage, (B1) (vinyl ester) is 9% to 55%, preferably up to 50%, more preferably up to 40%, even more preferably up to 35% and even more preferably up to 30%; Based on the total weight of the graft polymer in weight percentage, (B2) (nitrogen-containing monomer) is 1% to 41%, preferably up to 30%, more preferably up to 25%, such as 1% to 25% and more preferably 5% to 25%, even more preferably up to 15%, such as 1% to 15% and more preferably 5% to 15%, and further such as up to 10% to 40%, 35%, 20%, 10%, and each number between 1% and 41%, wherein preferably the amount of (B2) is not higher than the amount of (B1) Or - If (B2) is absent - (B) is 5% to 60%, preferably up to 50% and preferably 20%; Based on the total weight of the graft polymer in weight percentage, (B1) (vinyl ester) is the total amount of (B) minus the total amount of (B3), (B2) (nitrogen-containing monomer) is 0%, and a further prerequisite is that in all previous cases (B3) (additional monomer) is from 0% to 10%, preferably at most 2%, more preferably at most 1%, even more preferably about 0%, but in all cases at most 10% of the amount of (B1), and does not exceed the amount of (B2).

5. The graft polymer according to any one of claims 1 to 4, wherein at least 10 weight percent of the total amount of vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of vinyl ester can be any other known vinyl ester, wherein preferably at least 80 weight percent, more preferably at least 90 weight percent and most preferably substantially only vinyl acetate is used as the vinyl ester (weight percent based on the total weight of the vinyl ester monomer B1 employed).

6. The graft polymer according to any one of claims 1 to 5, wherein (A) the polyalkoxylate-ester backbone contains moieties derived from (i) alkylene oxide (AO), which contains at least one of ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO), preferably at least one of EO and PO wherein the amount of AO is 40 wt% to 99 wt%, preferably up to 90 wt%, and preferably 50 wt%, more preferably 60 wt% and even more preferably 70 wt%, and any value and range therebetween, each based on the total weight of the backbone the amount of EO is 0 wt.% to 100 wt.% based on the total AO, preferably 10 wt.%, more preferably 20 wt.%, even more preferably 30 wt.%, even more preferably 40 wt.%, such as 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.% or even 90 wt% the total amount of PO and / or BO is each 0 wt.% to 100 wt.%, preferably up to 90 wt.%, more preferably up to 80 wt.%, even more preferably up to 70 wt.%, even more preferably up to 60 wt.% and most preferably up to 50 wt.%, and any value therebetween, such as up to 5 wt.%, 10 wt.%, 15 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 55 wt.%, 65 wt.%, 75 wt.%, 85 wt.% or up to 95 wt.%, and more preferably 10 wt.%, even more preferably 20 wt.%, even further more preferably 30 wt.%, such as 40 wt.%, 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.% or even 90 wt%, each based on the total weight of AO, wherein for the sum of PO and BO, the total amount of PO and BO totals 100 wt.%, and wherein the total amount of AO totals 100 wt.%; (ii) Lactone / hydroxy acid monomer, in an amount of 1 wt.% and up to 60 wt.%, preferably up to 50 wt.%, more preferably up to 40 wt.%, most preferably up to 30 wt.%, and preferably 2 wt.%, more preferably 3 wt.%, even more preferably 4 wt.% and most preferably 5 wt.%, each based on the total weight of the main chain, preferably only caprolactone; Wherein the total weight of the sum of subunit (a1) and subunit (a2) in the main chain (A) totals 100 wt%.

7. The graft polymer according to claim 6, wherein, (i) The alkylene oxide (AO) is selected from ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO), preferably only EO and PO, Wherein the amount of the AO is 40 wt% to 99 wt%, preferably up to 90 wt%, and preferably 50 wt%, more preferably 60 wt% and even more preferably 70 wt%, and any value and range therebetween, each based on the total weight of the main chain, The amount of EO is 10 wt% to 90 wt% based on the total AO, preferably 20 wt% to 80 wt%, more preferably 30 wt% to 70 wt% and most preferably 40 wt% to 60 wt%, The total amount of PO and BO is 10 wt% to 90 wt%, preferably 20 wt% to 80 wt%, more preferably 30 wt% to 70 wt% and most preferably 40 wt% to 60 wt%, each based on the total weight of AO, wherein for the sum of PO and BO, the total amount of PO and BO totals 100 wt.%, and Wherein the total amount of AO totals 100 wt.%; (ii) The amount of lactone / hydroxy acid monomer is 1 wt.% and up to 60 wt.%, preferably up to 40 wt.%, more preferably up to 30 wt.%, even more preferably up to 25 wt.%, even further more preferably up to 20 wt.% and most preferably up to 15 wt.%, and preferably 2 wt.%, more preferably 3 wt.%, even more preferably 4 wt.% and most preferably 5 wt.%, each based on the total weight of the main chain, preferably only caprolactone; Wherein the total weight of the sum of subunit (a1) and subunit (a2) in the main chain (A) totals 100 wt%.

8. The graft polymer according to claim 6, wherein, (i) The alkylene oxide (AO) is selected from ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO), preferably only EO and PO, more preferably only EO The amount of EO is 20 wt% to 100 wt% based on the total AO, The total amount of PO and BO is from 0 wt.% to 80 wt.%, preferably up to 50 wt.%, more preferably up to 30 wt.%, even more preferably up to 20 wt.% and even further preferably up to 10 wt.% and most preferably zero, such as 45 wt.%, 45 wt.%, 45 wt.%, 25 wt.%, 15 wt.%, 7 wt.% and 5 wt.%, and any value therebetween, each based on the total weight of AO, wherein for the sum of PO and BO, the total amount of PO and BO totals 100 wt.%, wherein the total amount of AO totals 100 wt.%; (ii) The amount of lactone / hydroxyacid monomer is from 5 wt% and up to 50 wt%, preferably up to 40 wt%, more preferably up to 35 wt% and even more preferably up to 30 wt% based on the total weight of the main chain, and as a lower limit value preferably 7 wt%, more preferably 10 wt%, even more preferably 12 wt% and most preferably 15 wt%, such as 6 wt%, 8 wt%, 9 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt% and 15 wt% and any value therebetween as the lower limit value and such as 30 wt%, 33 wt%, 37 wt%, 45 wt% and any value therebetween as the upper limit value, preferably only caprolactone; wherein the total weight of the sum of subunit (a1) and subunit (a2) in the main chain (A) totals 100 wt%.

9. The graft polymer according to any one of claims 1 to 8, wherein, (B) These monomers are: (B1) At least one vinyl ester selected from vinyl acetate, vinyl propionate and / or vinyl laurate, the amount of which is from 70 wt% to 100 wt% by weight of the total weight of the monomers grafted onto the main chain (A), preferably only vinyl acetate, and (B2) Optionally at least one nitrogen-containing monomer, the amount of which is from 0 wt% to 30 wt% by weight of the total amount of the monomers grafted onto the main chain (A), which is preferably N-vinyl lactam, such as N-vinyl pyrrolidone, N-vinyl piperidone, N-vinyl caprolactam, even more preferably N-vinyl pyrrolidone and / or N-vinyl caprolactam, and most preferably N-vinyl pyrrolidone, wherein the vinyl ester monomer (B1) is optionally partially or completely hydrolyzed after polymerization.

10. The graft polymer according to any one of claims 1 to 9, wherein, Basically no other monomers (B2) and (B3) are used.

11. The graft polymer according to any one of claims 1 to 10, wherein, Monomers (B1) and (B2) are present and no other monomers are used.

12. The graft polymer according to any one of claims 1 to 11, wherein, After the polymerization reaction, at least a part of the vinyl ester-monomer (B1)-derived moiety is partially or completely hydrolyzed, preferably partially hydrolyzed, more preferably up to 50 mol%, preferably 20 mol%, more preferably from 20 mol% to 50 mol%, even more preferably from 30 mol% to 45 mol% based on the total number of moles of (B1) used, such as about 40 mol% hydrolysis.

13. The graft polymer according to any one of claims 1 to 12, wherein, which satisfies at least one of the following i), ii) and iii): i) These polymer backbones (A1), (A2) and (A3) may bear two hydroxyl groups as end groups or may be capped with a C1 to C22-alkyl group, preferably a C1 to C4 alkyl group; after the final preparation of the backbone, such end groups are attached using standard means, and for (A4), such capping is carried out on the oligomeric / polymeric subunit (a1) before the condensation polymerization of the subunit (a2); ii) The graft polymer has a polydispersity (PDI) Mw / Mn of at most 10, preferably at most 5, more preferably at most 3 and most preferably in the range of 1.0 to 2.6, and any value a as an upper or lower limit value and any range therebetween, such as 1.3 to 2.6, 1 to 3, etc. (where Mw = weight-average molecular weight and Mn = number-average molecular weight [g / mol / g / mol]); iii) The biodegradability of the graft polymer is at least 35%, more preferably at least 40%, even more preferably at least 45%, even further more preferably at least 50% within 28 days when tested according to OECD 301F, such as 46%, 47%, 48%, 49%, 50%, 55%, 60%, 65%, 70%, 75%, etc. and any value therebetween and up to 100%.

14. A method for obtaining a graft polymer according to one of claims 1 to 13, the method comprising the following steps: At least one vinyl ester monomer (B1), optionally at least one nitrogen-containing monomer (B2), and optionally additional monomers (B3) and further optionally additional monomers included as impurities in (B1), (B2) and / or (B3) are polymerized in the presence of at least one polymer backbone (A), wherein these polymer side chains (B) are obtained by radical polymerization, preferably using a radical-forming compound to initiate the radical polymerization.

15. The method according to claim 14, which comprises polymerizing at least one vinyl ester monomer (B1), optionally at least one nitrogen-containing monomer (B2), optionally further monomers (B3) in the presence of at least one polymer backbone (A) preferably selected from the main chains (A1), (A2), (A3) and (A4), a radical-forming initiator (C), and optionally at least one solvent (D) up to 50% by weight based on the sum of components (A), (B) and (C), at an average polymerization temperature at which the initiator (C) has a decomposition half-life of 40 to 500 min, in such a way that the fractions of unreacted graft monomers (B1), optional (B2) and optional (B3) and the initiator (C) in the reaction mixture remain continuously quantitatively deficient with respect to the polymer backbone (A), wherein preferably at least 10 weight percent of the total amount of the vinyl ester monomer (B1) is selected from vinyl acetate, vinyl propionate and vinyl laurate, more preferably selected from vinyl acetate and vinyl laurate, and most preferably vinyl acetate, and wherein the remaining amount of the vinyl ester can be any other known vinyl ester, wherein preferably at least 60, more preferably at least 70, even more preferably at least 80, even more preferably at least 90 weight percent and most preferably substantially only (i.e., about 100 wt.% or even 100 wt.%) vinyl acetate is used as the vinyl ester (weight percentages based on the total weight of the vinyl ester monomer B1 employed), and - preferably - the amounts of the monomers are those as described in any one of the claims listing such amounts as before.

16. The method according to any one of claims 14 or 15, wherein Substantially no other monomers (B3) are used.

17. The method according to any one of claims 14 to 16, wherein, Substantially no other monomers (B2) and (B3) are used.

18. The method according to any one of claims 14 to 17, wherein After the polymerization reaction, at least a part of the at least one vinyl ester - monomer (B1) - derived moiety preferably derived from only using vinyl acetate as (B1) is partially or completely hydrolyzed, preferably partially hydrolyzed, more preferably up to 50 mole percent and preferably 20 mole percent, more preferably 20 mole percent to 50 mole percent, even more preferably 30 mole percent to 45 mole percent, such as about 40 mole percent hydrolysis, based on the total moles of (B1) employed, and preferably no other monomers (B3) are used, more preferably N-vinyl lactam, preferably N-vinyl pyrrolidone is used as (B2).

19. The method according to any one of claims 14 to 18, wherein The method comprises at least one further method step selected from i) to iv): i) Post-polymerization; ii) Purification; iii) Concentration; and iv) Drying.

20. The method according to any one of claims 14 to 19, wherein The method comprises at least one further method step selected from the following: i) A post-polymerization process step, which is carried out after the main polymerization reaction, wherein an additional amount of initiator (optionally dissolved in the solvent) is preferably added over a period of 0.5 hour and up to 3 hours, preferably about 1 to 2 hours, more preferably about 1 hour, and the free radical initiator and the solvent for the initiator are typically - and preferably - the same as those used for the main polymerization reaction; and wherein after the polymerization reaction and before the post-polymerization reaction, preferably a period of time is waited during which the main polymerization reaction is allowed to continue, and then the post-polymerization reaction is started by beginning to add additional free radical initiator, such a period of time is preferably 10 minutes and up to 4 hours, preferably up to 2 hours, even more preferably up to 1 hour, and most preferably up to 30 minutes; and wherein the temperature of the post-polymerization process step is preferably the same as in the main polymerization reaction, or increased, compared to the temperature of the main polymerization reaction, such an increase is preferably about 5 °C to 40 °C higher, preferably 10 °C to 20 °C higher; ii) A step of subjecting the graft polymer obtained from the main polymerization or - if carried out - the post-polymerization process step to means of purification, concentration and / or drying to remove a part or almost all of the remaining solvent (as long as they are removable due to their boiling points) and / or volatiles such as residual monomers, wherein a. The concentration is carried out by preferably applying a distillation process such as thermal or vacuum distillation, preferably vacuum distillation, and / or by applying stripping with a gas such as steam or an inert gas such as nitrogen, preferably using steam from water, to remove a part of the solvent and optionally also volatiles - whereby this step additionally serves as a means for purification - to increase the solid polymer concentration - and optionally also for purification, carrying it out until the desired solid content and optionally also purity are obtained, preferably carrying it out until the desired part or all of the volatile components such as volatile solvents and / or unreacted volatile monomers are removed; b. The drying is carried out by subjecting the graft polymer containing at least a residual amount of volatiles such as remaining solvent and / or unreacted monomer, etc. to means for removing the volatiles, such as drying using rollers, spray dryer, vacuum drying or freeze drying, preferably - mainly for cost reasons - spray drying; and optionally combining such a drying process step with means for agglomeration or granulation to obtain agglomerated or granulated graft polymer particles, such a process is preferably selected from spray - agglomeration, granulation or drying in a fluidized bed dryer, spray - granulation device, etc.

21. The method according to any one of claims 14 to 20, wherein, The amount of water during the polymerization is at most 10 wt.%, preferably at most 5 wt.%, more preferably at most 1 wt.%, based on the total weight of the graft polymer (at the end of the polymerization) or based on the total weight of (A) and (B) (at the start of the polymerization).

22. Use of at least one graft polymer as described in any one of claims 1 to 13 or obtainable or obtained by a method as described in any one of claims 14 to 21 in a composition which is a fabric and home care product, a cleaning composition, an industrial and institutional cleaning product.

23. Use according to claim 22, which is a use in a cleaning composition and / or a fabric and home care product, preferably a cleaning composition for fabric and home care, which cleaning composition is preferably a laundry detergent formulation or a dishwashing detergent formulation, optionally further comprising at least one enzyme, which at least one enzyme is preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, deoxyribonucleases, xylanases, oxidoreductases, dispersing enzymes, mannanases and peroxidases, and combinations of at least two of the foregoing types, preferably at least one enzyme is selected from lipases, hydrolases, amylases, proteases, cellulases, wherein the at least one graft 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% relative to the total weight of such composition or product, and such product or composition further comprises a surfactant system in an amount of about 1% to about 70% by weight.

24. A composition which is a fabric and home care product, a cleaning composition, an industrial and institutional cleaning product, preferably a laundry detergent, a dishwashing composition, a cleaning composition and / or a fabric and home care product, each containing at least one graft polymer as described in any one of claims 1 to 13 or obtainable or obtained by a method as described in any one of claims 14 to 21, the cleaning composition being preferably a laundry detergent formulation or a dishwashing detergent formulation, optionally further comprising at least one enzyme, which at least one enzyme is preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, deoxyribonucleases, xylanases, oxidoreductases, dispersing enzymes, mannanases and peroxidases, and combinations of at least two of the foregoing types, preferably at least one enzyme is selected from lipases, hydrolases, amylases, proteases, cellulases, wherein the at least one graft 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% relative to the total weight of such composition or product, and such product or composition further comprises a surfactant system in an amount of about 1% to about 70% by weight.

25. The composition according to claim 24, further comprising 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.

26. The composition according to claim 24 or 25, 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.

27. A method of preserving the composition according to claim 25 against microbial contamination or growth, the method comprising adding an antimicrobial agent selected from the group consisting of 2-phenoxyethanol to the composition, the composition being an aqueous composition comprising water as a solvent.

28. A method for washing fabrics or cleaning hard surfaces, the method comprising treating the fabrics or hard surfaces with a composition according to claim 24 or 25, wherein, The composition comprises 4,4'-dichloro-2-hydroxydiphenyl ether, preferably 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.

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