Biodegradable graft polymers as dye transfer inhibitors

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 optionally (B1) at least one vinyl ester monomer, at least one, preferably at least two, nitrogen-containing monomers (B2), and optionally further monomers (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. These graft polymers are particularly used as dye transfer inhibitors in cleaning compositions.

Description

[0001] The present invention relates to novel graft polymers which are used, in particular, as dye transfer inhibitors in laundry applications, said graft polymers comprising 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 optionally at least one vinyl ester monomer (B1), at least one, preferably at least two, nitrogen-containing monomers (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 method for obtaining such a graft polymer, which method is preferably carried out by polycondensation. Furthermore, the present invention relates to the use of such a graft polymer in, for example, fabrics and household care products. Another subject of the present invention is a composition comprising at least one graft polymer, such as fabrics 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 intense dialogue about future requirements for soluble polymers used in consumer products. Therefore, there is a high expectation to identify new and better biodegradable components for such applications. This problem is very serious for polymers produced by free radical polymerization based on only a carbon 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 a free radical method having 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] When washing fabrics, dye transfer can pose challenges, such as dyes from one part of the fabric may be suspended in the wash liquor and may then deposit on a different part of the fabric, or entirely on a different fabric. The transfer of such dyes (referred to as "bleed dyes") can lead to dye graying and discoloration of the fabric, especially those of light or white color.

[0005] Certain polymers, commonly referred to as dye transfer inhibitors / inhibiting polymers ("DTI"-polymers; "DTI" is also used for "dye transfer inhibition"), have been conventionally used in laundry compositions to address the problem of dye transfer. Such polymers include poly-1-vinylpyrrolidone (PVP), poly(vinylpyridine-N-oxide) (PVNO), poly-1-vinylpyrrolidone-co-1-vinylimidazole (PVPVI), and polyvinylpyrrolidone(vinylpyridine-N-oxide) (PVPVNO) polymers, which typically include relatively high levels of 1-vinylpyrrolidone ("VP"). These conventional DTI polymers are quite effective in inhibiting the transfer of direct dyes, but are non-biodegradable due to their carbon-carbon backbone that cannot be successfully attacked by microorganisms.

[0006] Copolymers of 1-vinylimidazole and 1-vinylpyrrolidone and their use as effective dye transfer inhibitors (DTIs) in laundry applications (liquid, gel, and solid color care detergents) are well-known (such as " HP 56" of BASF) and are considered the "gold standard". Those polymers show excellent dye transfer inhibition at very low amounts, but - like all the other known DTI-polymers mentioned above - are not biodegradable in any significant amount because they also have a carbon-carbon bonded polymer backbone.

[0007] However, since a certain amount of consumer products containing such polymers are rinsed away after their use and may end up in rivers or oceans if not biodegraded or otherwise removed in sewage treatment plants, biodegradation of such polymers for detergent applications is highly desirable.

[0008] Therefore, it is highly desirable to identify better biodegradable components for such applications.

[0009] The problem of poor biodegradability is very serious for polymers produced by free radical polymerization based on a carbon-only backbone (i.e., a backbone that does not contain heteroatoms such as oxygen or nitrogen), because a carbon-only backbone is particularly difficult for microorganisms to degrade. Even graft polymers produced by free radical methods with a polyethylene glycol backbone of industrial importance show only limited biodegradation in wastewater.

[0010] Low molecular weight polyethylene oxide with a Mw of 600 g / mol is known to be readily biodegradable, while polyethylene oxide with a Mw of 6000 g / mol has only poor biodegradability. BASF's The safety data sheet of E 600 (Rev. 2.0, dated January 05, 2021) confirms polyethylene glycol with Mw = 600 g / mol and a DOC value (dissolved organic carbon) > 70% measured according to OECD 301A. In comparison, the safety data sheet of BASF's E 6000 granules (Rev. 2.0, dated August 10, 2018) mentions that polyethylene glycol with Mw = 6000 g / mol has very poor biodegradability, showing only 10 - 20% CO2 formation relative to the theoretical value (60 days) according to OECD 301B.

[0011] Various further attempts have been made to provide DTI - polymers with properties similar to those of the copolymer of 1 - vinylimidazole and 1 - vinylpyrrolidone, but none have achieved similar DTI performance or useful biodegradability / nor achieved useful biodegradability.

[0012] 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).

[0013] Similarly, graft polymers of vinyl esters grafted onto polyalkylene oxide - polymers such as vinyl acetate - graft - polyethylene glycol are known polymers. Their applications in the detergent field and many other application fields are also known.

[0014] However, those polymers lack biodegradability or at least suffer from very limited biodegradability.

[0015] However, a certain amount - if not all - of such consumer products are ultimately rinsed away after their use, and if not biodegraded or otherwise removed in a sewage treatment plant, they may ultimately end up in rivers or the ocean.

[0016] 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.

[0017] According to the applicable laws of certain countries (if not yet implemented and effective, it is expected to become law in the near future), such problems will no longer be acceptable.

[0018] 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.

[0019] Therefore, it is of utmost importance to provide biodegradable polymers for the detergent field to solve the environmental pollution problem without compromising cleaning efficiency, as such lower cleaning efficiency would not only inevitably pollute the environment.

[0020] The poor biodegradability of polyalkylene oxides decreases in the range from several hundred g / mol to several thousand g / mol of molecular weight. Even more so, graft polymers based on such polyalkylene oxides are usually even worse in terms of biodegradation due to grafting.

[0021] Prior art graft polymers

[0022] WO 03 / 042262 relates to a “graft polymer” which comprises (A) a polymer graft backbone without monoethylenically unsaturated units and (B) a polymer side chain formed from a copolymer of two different monoethylenically unsaturated monomers (B1) and (B2) each containing a nitrogen heterocycle, wherein the proportion of the side chain (B) totals 35 to 55 wt.% of the total polymer.

[0023] However, the graft polymers according to WO 03 / 042262 do employ larger amounts of vinylimidazole and vinylpyrrolidone monomers for the production of the corresponding polymer side chains grafted onto the main chain. The DTI properties of those polymers are acceptable but still far from the gold standard. Biodegradation is not mentioned. Given the higher amounts of vinyl monomers, the production costs are also higher.

[0024] US A 5,318,719 relates to a class of biodegradable water-soluble graft copolymers having builder, anti-filming, dispersing and threshold crystal inhibition properties, which comprise (a) acid-functional monomers and optionally (b) other water-soluble monoethylenically unsaturated monomers copolymerizable with (a) grafted onto a biodegradable substrate comprising polyalkylene oxides and / or polyalkoxylated materials. However, US-A 5,318,719 does have to employ large amounts of acid-functional monomers such as acrylic acid or methacrylic acid to produce the side chains of the graft polymers. Such types of acid monomers are not available in the context of the present invention as they would disrupt the DTI action of the amine-(imidazole) groups and lactam groups.

[0025] US 2019 / 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, US 2019 / 0390142 does not disclose additional nitrogen-containing monomers such as vinylimidazole. Moreover, the amounts of the main chain and monomers used and the intended uses are different.

[0026] WO 2007 / 138053 discloses an amphiphilic graft polymer based on a water-soluble polyalkylene oxide (A) as the graft matrix and side chains (B) formed by the polymerization of a vinyl ester component, the polymer having an average of less than one graft site per 50 alkylene oxide units and an average molar mass M of 3,000 to 100,000. However, WO 2007 / 138053 does not contain any disclosure regarding the biodegradability of the corresponding graft polymers disclosed therein, nor does it disclose any significant amount of nitrogen-containing monomers.

[0027] WO 2021160795 A1 relates to a graft polymer which comprises a block copolymer main chain (A) as the graft matrix onto which polymer side chains (B) are grafted. These polymer side chains (B) can be obtained by the polymerization of at least one vinyl ester monomer (B1) and optionally N-vinylpyrrolidone as an optional additional monomer (B2). Most preferably, the block copolymer main chain (A) is a triblock copolymer of polyethylene oxide (PEG) and polypropylene oxide (PPG). The invention further relates to the use of such graft polymers in, for example, fabric and household care products. However, no other monomers are included except for the monomer vinylpyrrolidone included only as "optional" and the required vinyl ester monomer, specifically no vinylimidazole monomer is included. Nor is there any mention of the application as DTI.

[0028] WO 2020 / 005476 discloses fabric care compositions comprising graft copolymers and so-called processing aids, the 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 the main chain, and wherein the main chain and the two monomers are in specific ratios. Vinyl imidazole is not disclosed as a monomer. However, as the target application of the fabric care composition of the present invention, DTI is mentioned; it is not explicitly disclosed that the graft polymer itself is explicitly used as a DTI-polymer, except for the following "viewpoint": if the molecular weight of the graft matrix such as polyethylene glycol is relatively low, there may be a decrease in the performance of dye transfer inhibition, and when the molecular weight is too high, the polymer may not remain suspended in the solution and / or may deposit on the treated fabric. The DTI-performance seems to be attributed to the specific combination of the claimed compounds rather than the graft polymer itself alone. Moreover, the additional "processing aids" mentioned as preferred components are known DTI-polymers as mentioned in the general prior art level known to those skilled in the art as above.

[0029] 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.

[0030] This disclosure discloses so-called "suspension graft copolymers" selected from the group consisting of poly(vinyl acetate)-g-poly(ethylene glycol), poly(vinyl pyrrolidone)-poly(vinyl acetate)-g-poly(ethylene glycol) and combinations thereof, and thus does not include vinyl imidazole as a monomer. In addition, specifically claimed is that in addition to the suspension graft polymer, typical known dye transfer inhibitor-polymers (those mentioned in the general prior art level known to those skilled in the art as above) are also included in the claimed fabric cleaning composition.

[0031] WO 0018375 discloses pharmaceutical compositions comprising graft polymers obtained by the polymerization of vinyl esters of at least one aliphatic C1-C24-carboxylic acid in the presence of a polyether, wherein the vinyl ester is preferably vinyl acetate. In the most preferred variant, the graft polymer is prepared by grafting vinyl acetate onto PEG with a Mw of 6000 g / mol and then hydrolyzing the vinyl acetate to an alcohol (which will then be similar to a polymer obtained from the hypothetical monomer "vinyl alcohol"). The main use is to form coatings and films on solid pharmaceutical dosage forms such as tablets and the like.

[0032] However, WO 0018375 also claims polymers obtained by the polymerization of vinyl esters of at least one aliphatic C1-C6-carboxylic acid in the presence of a polyether, where at least one monomer is selected from the group consisting of: c1) C1-C6-alkyl esters of monoethylenically unsaturated C3-C8-carboxylic acids; c4) N-vinylpyrrolidone, N-vinylimidazole, N-vinylcaprolactam; c5) (meth)acrylic acid.

[0033] WO 0018375 also claims polymers in which, in addition to the vinyl ester, at least one other monomer c) selected from the group consisting of: c1) C1-C24-alkyl esters of monoethylenically unsaturated C3-C8-carboxylic acids; c2) C1-C24-hydroxyalkyl esters of monoethylenically unsaturated C3-C8-carboxylic acids; c3) C1-C24-alkyl vinyl ethers; c4) N-vinyl lactams; c5) monoethylenically unsaturated C3-C8-carboxylic acids is used for the polymerization.

[0034] WO 0018375 further claims polymers in which, in addition to the vinyl ester, at least one other monomer c) selected from the group consisting of: c1) C1-C6-alkyl esters of monoethylenically unsaturated C3-C8-carboxylic acids; c4) N-vinylpyrrolidone, N-vinylimidazole, N-vinylcaprolactam; c5) (meth)acrylic acid is used for the polymerization.

[0035] As the polymer backbone, WO 0018375 discloses polyethers having a number average molecular weight in the range below 500,000, preferably in the range of 300 to 100,000, particularly preferably in the range of 500 to 20,000, very particularly preferably in the range of 800 to 15,000 g / mol. Further mentioned is that advantageously homopolymers of ethylene oxide or copolymers with an ethylene oxide content of 40% to 99% by weight are used and thus preferably an ethylene oxide unit content of 40 mol% to 100 mol% is used in the ethylene oxide polymers. It is said that suitable comonomers for these copolymers are propylene oxide, butylene oxide and / or isobutylene oxide, and suitable examples are given as copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide, and copolymers of ethylene oxide, propylene oxide and at least one butylene oxide. It is alleged that the ethylene oxide content in the copolymer is preferably 40 to 99 mol%, the propylene oxide content is 1 to 60 mol% and the butylene oxide content in the copolymer is 1 to 30 mol%. It is said that not only linear but also branched homopolymers or copolymers can be used as the grafting matrix for grafting.

[0036] However, only PEG 6000 and 9000, "polyethylene glycol / polypropylene glycol block copolymer" (average molecular weight "about 8000") and "polyglycerol" (average molecular weight "2200") (all in g / mol) are exemplified in WO 0018375. Five examples use only vinyl acetate, and only one example uses vinyl acetate and methyl methacrylate as monomers. No other monomers are exemplified. All examples use hydrolysis of the polymerized vinyl acetate monomer as the final step.

[0037] Therefore, there is no production and characterization in WO 0018375 of polymers that do not contain vinyl ester monomers but contain the additionally required monomers as claimed in the present invention.

[0038] WO 0018375 also does not disclose the use of such polymers as disclosed herein for detergent and cleaning or fabric care applications, and specifically does not disclose the use as DTI-polymers. There is no mention at all in this disclosure of such applications or uses.

[0039] US2008 / 255326 discloses a method for preparing a graft polymer that comprises a polyalkylene oxide polymer such as polyethylene glycol as a graft matrix, vinyl esters such as vinyl acetate and vinyl lactams such as vinyl pyrrolidone (both grafted onto the polyalkylene oxide backbone), and optionally a monomer from a third class ("monomer c"), the amount of which is from zero to up to 10 (ten) weight percent based on the total amount of graft monomers, wherein the total amount of graft monomers totals 100 weight percent, and the amount of all graft monomers is from 10 to 95 weight percent based on the total weight of the resulting graft polymer. However, the present invention is using vinyl acetate or any other vinyl ester monomer.

[0040] US2019 / 390142 A1 does not disclose a graft polymer comprising vinyl imidazole as a monomer, nor any other amine-containing monomer as required by the present invention. Moreover, it does not disclose the use of the disclosed graft polymer for inhibiting dye transfer during washing. The only polymers containing vinyl imidazole mentioned as dye transfer inhibitors in the disclosed compositions are known copolymers of vinyl imidazole and vinyl pyrrolidone such as Sokalan HP 56, i.e., standard linear copolymers of these two monomers.

[0041] US 31816566 discloses graft polymers of so-called "lactone polyesters" and their blends with PVC. Lactone polyesters are homopolymers of ε-caprolactone or copolyesters thereof with ε-alkyl-ε-caprolactones. Polymers made from lactones and alkylene oxides, which are 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 that the graft polymerization is actually carried out using acrylic acid, butyl acrylate, dimethylamino ester of methacrylic acid, styrene, acrylonitrile and methyl methacrylate as the only monomers, all only as single monomers and without using monomer mixtures. Only one example (Example 12) uses vinyl acetate as the monomer and poly-ε-caprolactone as the graft matrix (i.e., a graft matrix that does not contain any alkylene oxide), with 200 g of the main chain and 30 g of vinyl acetate, that is, the amount of vinyl acetate based on the graft matrix is 15 wt.%, which is equal to 13 wt.% of vinyl acetate based on the total polymer weight. US 31816566 does not disclose any content regarding the biodegradation of such polymers; the only use disclosure is as a plasticizer in PVC polymers. The graft polymers of the type shown in the present invention are not disclosed nor indicated.

[0042] WO 2022 / 136409 of BASF discloses amphiphilic alkoxylated polyalkyleneimines or amines; graft polymers containing polymers made from lactones and alkylene oxides as graft backbones grafted with ethylenically unsaturated monomers containing at least vinyl esters in free radical polymerization are not disclosed. Therefore, his disclosure is completely irrelevant to the present invention, except for the fact that it also targets polymer structures for use in fields similar to those of the present invention and those products contain lactones and alkylene oxides. The lactones and alkylene oxides are polymerized to produce lactone-alkylene oxide-copolymers, which are attached to the amine groups of the starting compound polyethyleneimine or polyamine. After the formation of those side chains, graft polymerization is not carried out. Therefore, these structures and 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 not disclosed nor indicated.

[0043] 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 preferably mentioned " HP22” - which does not contain lactones in its entire polymer backbone, so that such a backbone is made only of alkylene oxides. Those alkylene oxides - and in particular the preferred polymers with a backbone molecular weight of about 6000 g / mol - are not very biodegradable at all, and graft polymers are prepared using such polyalkylene oxide - backbones with even worse biodegradability as shown in the present invention. Graft polymers of the type shown in the present invention are not disclosed nor indicated.

[0044] At the time of filing the present invention, the task of improving the biodegradability of graft polymers based on a backbone with polyalkylene oxide - units in the backbone had 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 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.

[0045] The polymers in this disclosure are subject to a two - step synthesis of the backbone: 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 mixture obtained contains unoxidized starting materials, polyalkylene oxides with one hydroxyl group oxidized to a carboxyl functional group, and polyalkylene oxides with both ends oxidized. Thus, the flexibility in designing the backbone is highly restricted.

[0046] This patent application also does not disclose the use of nitrogen - containing monomers for the preparation of graft polymers.

[0047] Prior art regarding the main chain

[0048] The present invention discloses the use of three main types of polymer backbones comprising (oligo - / poly -) alkylene oxide moieties and (oligo - / poly -) lactone / hydroxy - acid - derived moieties.

[0049] Such backbones are designated (A1), (A2) and (A3) (see the following definitions) and are in principle known hitherto:

[0050] (A1)

[0051] WO 2002046268 (Cognis, now BASF) discloses biodegradable polymers as surfactants, emulsifiers, etc., which are obtained by reacting an organic initiator with 1. alkylene oxide, 2. a mixture of alkylene oxide and lactone. "Organic initiator" is defined on page 4 as a mono - functional or multi - functional alcohol or amine.

[0052] To obtain a copolymer from an alkylene oxide and a caprolactone, a suitable initiator is reacted with a premixed combination of an alkylene oxide and a caprolactone.

[0053] To obtain an (A1)-backbone type copolymer from an alkylene oxide and a lactone such as caprolactone, a suitable initiator is reacted with a premixed combination of an alkylene oxide and a caprolactone.

[0054] An alcohol having 2 hydroxyl groups (diol) is used as the initiator. 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.

[0055] The alkylene oxides combined with caprolactone used are: ethylene oxide, 1,2-epoxypropane or 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxypentane, preferably ethylene oxide and propylene oxide.

[0056] The copolymerization of an alkylene oxide and a caprolactone is carried out under typical conditions for alkoxylation reactions. Basic catalysts such as potassium hydroxide, sodium hydroxide, sodium methoxide, and potassium methoxide are used.

[0057] (A2)-backbone type polymers can in principle be obtained by the alkoxylation of a polyester.

[0058] The polyester is obtainable, for example, by polymerizing a lactone such as caprolactone onto an initiator having 2 hydroxyl groups (such as a diol 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.).

[0059] The polymerization of caprolactone is carried out with various catalysts such as the transesterification catalyst tin(II) alkanoate.

[0060] The alkoxylation of such polycaprolactone is carried out under typical alkoxylation conditions. Due to the basic reaction conditions for alkoxylation, a transesterification reaction can occur at the ester bond of the polycaprolactone.

[0061] US 4281172 describes acrylates from polyester-polyether copolymers. To obtain these structures, a polyester of a monoalcohol, diol, triol, or tetraol is reacted with an alkylene oxide.

[0062] The polyester esters are synthesized according to US 3169945 from a hydroxyl group-containing component with various catalysts (including Ti or Sn catalysts or alkali metal hydroxides).

[0063] The alkoxylation reaction is catalyzed by BF3-etherate or potassium hydroxide, etc.

[0064] JP 07149883 describes a method for obtaining a polyester-polyol by reacting a compound having at least two active hydrogens with a lactone and then with an alkylene oxide. Both reactions are carried out using the same catalyst. The catalyst is an alkali metal hydroxide or an alkali metal alkoxide.

[0065] WO 9636656 claims biodegradable alkylene oxide-lactone copolymers. These polymers are synthesized from bifunctional or polyfunctional starters by reacting the starters with alkylene oxide and lactone in a copolymerization reaction and then block-capping with alkylene oxide. 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 backbone for graft polymers.

[0066] (A3)-type main-chain polymers can in principle be obtained by the polycondensation of polyalkylene glycols with lactones, resulting in - simplified - triblock polymers.

[0067] Triblock copolymers having an intermediate polyalkylene oxide block and derived from caprolactone and alkylene oxide are 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.

[0068] Both reactions can be carried out under the typical reaction conditions for the alkoxylation reaction (polyalkoxylate) and for the polymerization of caprolactone (polycaprolactone block).

[0069] Such triblock copolymers having an intermediate poly(ethylene oxide) block have been known since about the 1990s. For drug release and dissolution purposes, these polymers are used (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).

[0070] (A4)-type main chains are also known:

[0071] WO 96 / 36656 discloses biodegradable oxide-lactone copolymers and copolyesters as already described above for (A3).

[0072] WO 2002046268 (Cognis Corporation, now BASF Corporation) discloses alkylene oxide-lactone copolymers as already described for (A1).

[0073] However, unknown is the use of such polymers as the backbone for graft polymers, which would introduce improved biodegradability into such graft polymers via the backbone.

[0074] Object of the invention

[0075] It has been recognized that graft polymers based on conventional polyalkylene oxides (without ester groups in the backbone) show unexpectedly low biodegradation, which is generally much lower than the expected biodegradation percentage calculated based on the biodegradation of pure polyalkylene oxides.

[0076] 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 (usually a polyalkylene glycol having two hydroxyl end groups and thus such polyalkylene glycols having hydroxyl groups are generally referred to as “polyalkylene glycols”) grafted to such a backbone via free radicals with polymerizable monomers (i.e., the number of side chains on the backbone increases). This is sometimes attributed to the blocking of the biodegradation mechanism because it appears that polyalkylene oxides / polyalkylene glycols degrade 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 the degradation. Thus, it has been 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 has also generally been observed that with increasing degree of branching, there is an improvement in performance in the desired applications because only when the amount of side chains is higher does the change in the chemical structure of the backbone become 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.

[0077] 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.

[0078] Although the unpublished patent application PCT / EP 2022 / 065983 has provided a first solution to the problem of the 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 since two completely different types of chemical reactions (oxidation and polymerization) are employed and the structural changes are not easily controlled, because the oxidation results in a mixture of compounds such as diols (i.e., starting material polyalkylene glycols), monoalcohol-monoacids (i.e., partially oxidized polyalkylene glycols), and dicarboxy-polyalkylene oxides (i.e., completely oxidized polyalkylene glycols). Structures as used herein are not obtainable by the methods disclosed in this document. Similarly, nitrogen-containing monomers are not disclosed.

[0079] Therefore, there is a need to improve the biodegradation of conventional graft polymers based on polyalkylene oxides by improving the biodegradability of the graft matrix and maintaining the general structure of the graft polymer and thus maintaining the application properties or even improving them, and to improve the cost and efficiency of the unpublished patent application PCT / EP 2022 / 065983 by reducing the production method to only one reaction step employing only one type of reaction and simultaneously improving the variability of the chemical structure.

[0080] Although polymers of types (A1), (A2), and (A3) as defined herein are known, their use as a backbone for preparing graft polymers is not yet known.

[0081] Therefore, an object of the present invention is to provide novel graft polymers based on a graft backbone of the polyalkylene oxide type that confers ester functional groups.

[0082] 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.

[0083] Graft polymers

[0084] The graft polymer of the present invention comprises The polymer main chain as a grafting matrix as the first structural unit and Poly The polymer side chain as the second structural unit .

[0085] The first structural unit (main chain)

[0086] The first structural unit of the graft polymer is a polymer backbone serving as a graft matrix for the graft polymer of the present invention, wherein the polymer backbone (A) is obtainable by the polymerization of at least one subunit (a1) and at least one subunit (a2).

[0087] The subunit (a1) is made of at least one alkylene oxide monomer and / or at least one polyalkylene oxide-polymer having two hydroxy end groups The 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-epoxypropane, 1,2-epoxybutane, 2,3-epoxybutane, 1,2-epoxypentane or 2,3-epoxypentane; selected from 1,4-diols or their cyclic or oligomeric analogues, or polymeric ethers based on such 1,4-diols; selected from 1,6-diols or their cyclic or oligomeric analogues, 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.

[0088] As used herein, the term "block (co)polymer" means that the corresponding polymer comprises 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" comprises n different blocks (homopolymer and / or copolymer subunits). In a single block, the size / length of such a block 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).

[0089] Preferably, at least one monomer in the polymer is derived from the use of ethylene oxide.

[0090] 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 consisting of two or more alkylene oxides, where one of the monomers is ethylene oxide. Preferably, in addition to ethylene oxide, the additional monomer is propylene oxide (PO) and / or 1,2-epoxybutane (BO), preferably only 1,2-propylene oxide.

[0091] The similarity of (A1), (A2) and (A3)

[0092] The at least one lactone and / or hydroxy acid is selected from group i) and / or ii), where

[0093] 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;

[0094] and

[0095] 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, and lactic acid, glycolic acid, 4-hydroxybutyric acid, 6-hydroxyhexanoic acid, 12-hydroxystearic acid, citric acid;

[0096] Preferably lactic acid or caprolactone, more preferably caprolactone.

[0097] 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.

[0098] 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 that

[0099] -1) a first defined (a1)-subunit is obtained and then reacted with the (a2)-subunit,

[0100] -2) the monomeric alkylene oxide from subunit (a1) is reacted directly with the monomer subunit (a2); or

[0101] -3) Combine the previous methods 1) and 2).

[0102] Thus, three main backbone structures can be defined and obtained:

[0103] (A1):

[0104] The subunit (a2) can be added during the polymerization of the alkylene oxide (a1-unit) to produce a random copolymer; in a variant thereof, a polyalkylene oxide having two hydroxyl groups can be added to such a polymerization, thereby introducing a specific (a1)-subunit-block; this variant is applicable if the alkylene oxide used is at least partially different from the alkylene oxide used for the preparation of 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.

[0105] 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.

[0106] Structures such as the following can be obtained by this method:

[0107] Poly[random-{lactone}-{alkylene oxide}]

[0108] ("Oligo / poly lactone" depicts the (a2)-subunit and is thus prepared from lactone / hydroxy acid; "PAG" = polyalkylene glycol is used here to depict the (a1)-subunit)

[0109] Therefore, in a preferred embodiment, the polymer backbone is selected from

[0110] (A1) A backbone consisting of a random arrangement order of monomeric, oligomeric, and / or polymeric (a1)-subunits and monomeric, oligomeric, and / or polymeric (a2)-subunits, wherein there are more than one subunit (a1) and / or more than one subunit (a2).

[0111] (A2):

[0112] 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 modified by adjusting the amount and length of the (a2)-subunit-chains within the (A2)-backbone.

[0113] As in (A1), in its further variants, polyalkylene oxides having two hydroxyl groups can also be added to such polymerization, thereby also introducing specific (a1)-subunit-blocks; this variant is applicable if the alkylene oxide used is at least partly different from the alkylene oxide used for preparing the polyalkylene oxide also employed, 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 to be copolymerized with (a2)-subunits and the polyalkylene oxide.

[0114] In a simplified approach, the (A2)-main chain can be described as a triblock polymer having an internal (a2)-block and two external (a1)-blocks.

[0115] (Switching the order to the opposite direction gives structure (A3); see below.)

[0116] Structures of the form shown below (in its simplest form) can be obtained by this method:

[0117] [PAG]-[oligo / polyester]-[PAG]

[0118] (Here, "lactone" is used to denote the (a2)-subunit and thus is made of lactone / hydroxy acid and can be a single monomer unit or an oligomeric or polymeric unit made of monomers in the first reaction step; "PAG" = polyalkylene glycol is used here to depict the (a1)-subunit)

[0119] In the case where the (a2)-subunit-starting material has not completely reacted upon addition of 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.

[0120] Thus, in a preferred embodiment, the polymer main chain is selected from main chains 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 pentablock, heptablock, and nonablock, 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.

[0121] (A3):

[0122] 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 a structure 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.

[0123] 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:

[0124] (Switching the order to the opposite direction gives structure (A2); see above.)

[0125] [Oligomer / polyester]-[PAG]-[Oligomer / polyester]

[0126] ("Oligomer / polyester" 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)

[0127] Thus, in a preferred embodiment, the polymer main chain is selected from the main chain of (A3) consisting 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)]-”.

[0128] 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.

[0129] The second structural unit (grafted side chain)

[0130] 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.

[0131] 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).

[0132] 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.

[0133] 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.

[0134] (A4):

[0135] (A4) is a structure starting from an oligomeric or polymeric subunit (a1) which 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 subsequently 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

[0136] [capping group]-[subunit (a1)]-[subunit (a2)], or

[0137] [capping group]-[subunit (a1)]-[random-{subunit (a2)-subunit (a1)}].

[0138] It should be emphasized that the oligomerization or polymerization of subunits (a1) and (a2) can each be achieved by using “starter molecules” which are then incorporated into the oligomers and polymers of subunits (a1) and (a2). Suitable starter 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 starter molecule for the condensation of alkylene oxides.

[0139] Thus, the backbones (A1) to (A4) can contain portions derived from such starter 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.

[0140] In cases where compounds derived from alkylene oxides are used as starting molecules, such uses have been described in the above main chain definitions, and thus such starting molecules derived from alkylene oxides can be added as molecules or - in the case of oligomers or polymers of alkylene oxides - 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).

[0141] A typical reaction procedure for obtaining such structures is, first, to form an oligo / polyalkoxylate from a 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).

[0142] The polymerization of the subunit (a2) is carried out in a known manner with various catalysts such as the transesterification catalyst tin(II) alkanoate.

[0143] 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.

[0144] In a preferred embodiment, the polymer main chain as the graft matrix comprises at least one subunit (a1) and at least one subunit (a2), where

[0145] (a1) is a unit comprising (preferably consisting essentially of) a moiety derived from at least one alkylene oxide monomer and / or at least one polyalkylene oxide-polymer having two hydroxy end groups, the alkylene oxide monomers being selected from the group of C2- to C10-alkylene oxides, preferably C2 to C5-alkylene oxides,

[0146] (a2) is a unit comprising at least one lactone and / or at least one hydroxy acid (preferably consisting of), such 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,

[0147] where preferably the at least one lactone and / or hydroxy acid is selected from group i) and / or ii), where

[0148] 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;

[0149] and

[0150] 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;

[0151] preferably lactic acid or caprolactone, more preferably caprolactone,

[0152] wherein the polymer backbone is obtained by

[0153] (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);

[0154] (A2) first oligomerizing / polymerizing the subunit (a2), and then polymerizing the product with the subunit (a1);

[0155] (A3) first oligomerizing / polymerizing the subunit (a1), and then copolymerizing the product with the subunit (a2); or

[0156] (A4) first providing 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 portions 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)}];

[0157] Where there are already more than one subunit (a1) and / or more than one subunit (a2) present in the oligomer or polymer employed, those subunits may be arranged in any order within such employed oligomer or polymer, and

[0158] where there are more than one subunit (a1) and / or more than one subunit (a2) available for polymerization, those subunits (and optionally the oligomer / polymer, if employed) may be arranged in any order within the resulting main chain,

[0159] and where - optionally - at least one starting molecule is incorporated into the main chain structure. The polymer main chain (A) and in particular (A1), (A2) and (A3) may optionally be capped at the end groups, the capping being effected by known techniques using C1-C25 alkyl groups, preferably C1 to C4 groups. Such capping will be carried out after the main chain has been produced and may preferably be carried out before grafting.

[0160] In the case of (A4), capping at 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).

[0161] When preparing oligoalkylene oxide / polyalkylene oxide as the starting block, a diol may be used as the starting molecule for preparing the oligoalkylene oxide / polyalkylene oxide, so that such an oligomer / polymer of subunit (a1) may contain in its structure a moiety derived from such a diol. Diols for such use and methods for preparing such oligoalkylene oxide / polyalkylene oxide 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.

[0162] 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

[0163] (a1) is a unit containing (preferably consisting essentially of) a moiety derived from at least one alkylene oxide monomer and / or at least one polyalkylene oxide-polymer having two hydroxyl end groups, the alkylene oxide monomers being selected from the group of C2- to C10-alkylene oxides, preferably C2 to C5-alkylene oxides,

[0164] (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 part 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,

[0165] wherein preferably the at least one lactone and / or hydroxy acid is selected from group i) and / or ii), wherein

[0166] 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;

[0167] and

[0168] 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;

[0169] Preferably lactic acid or caprolactone, more preferably caprolactone,

[0170] wherein the polymer backbone as the grafting matrix (A) is selected from

[0171] (A1) A backbone consisting of randomly arranged monomeric, oligomeric and / or polymeric (a1)-subunits and monomeric, oligomeric and / or polymeric (a2)-subunits, wherein there are more than one subunit (a1) and / or more than one subunit (a2);

[0172] (A2) A backbone consisting of an oligomeric subunit or polymeric subunit (a2) as an 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 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.;

[0173] (A3) A main chain composed of an inner 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

[0174] (A4) A main chain composed of:

[0175] A first block having

[0176] (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

[0177] (ii) Oligomeric or polymeric subunits (a1); and

[0178] 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),

[0179] 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,

[0180] Such a diblock structure has the following as an idealized structure when only using subunit (a2) for the second block: [capping group]-[subunit (a1)]-[subunit (a2)]

[0181] Or has the following as an idealized structure when using subunits (a1) and (a2) for the second block:

[0182] [capping group]-[subunit (a1)]-[random-{subunit (a2)-subunit (a1)}.

[0183] 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.

[0184] Preferably, the polyalkoxylate - ester main chain contains moieties derived from

[0185] (i) An alkylene oxide (AO) which includes at least one of ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO), preferably at least one of EO and PO,

[0186] wherein the amount of 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.

[0187] 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.

[0188] 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.%.

[0189] (ii) 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.

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

[0191] 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 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; 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.

[0192] In an alternative but preferred embodiment, at least two different alkylene oxides are employed for preparing the main chain / present in the main chain.

[0193] Thus, in a more preferred embodiment, the polymer main chain consists of

[0194] (i) alkylene oxide (AO), which is selected from ethylene oxide (EO), propylene oxide (PO) and butylene oxide (BO), preferably only EO and PO,

[0195] The amount of EO 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%, based on the total AO,

[0196] 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, where for the sum of PO and BO, the total amount of PO and BO totals 100 wt.%, and

[0197] where the total amount of AO totals 100 wt.%;

[0198] (ii) lactone / hydroxy acid monomer, the amount of which 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;

[0199] where the total weight of the sum of the subunit (a1) and the subunit (a2) in the main chain (A) totals 100 wt%,

[0200] and wherein in the case of (A1), (A2) and (A3), the use of the starting molecule is optional.

[0201] Thus, in a more preferred alternative embodiment, the polymer backbone consists of

[0202] (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

[0203] The amount of EO is 20 wt% to 100 wt% based on the total AO,

[0204] 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.%,

[0205] wherein the total amount of AO totals 100 wt.%;

[0206] (ii) lactone / hydroxy acid monomer, the amount of which 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;

[0207] wherein the total weight of the sum of subunit (a1) and subunit (a2) in backbone (A) totals 100 wt%,

[0208] and wherein in the case of (A1), (A2) and (A3), the use of the starting molecule is optional.

[0209] In an even more preferred embodiment, the backbone for any embodiment of the graft polymer of the present invention as defined herein is a structure selected from structures (A1), (A2), (A3) and / or (A4).

[0210] The second structural unit of the graft polymer

[0211] 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), at least one, preferably at least two nitrogen-containing monomers (B2), optionally further monomers (B3), and optionally further monomers in addition to (B1), (B2) and (B3).

[0212] 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 can be used, such as C4 to C16-vinyl esters, such as vinyl valerate, vinyl pivalate, vinyl neodecanoate, vinyl decanoate, and / or vinyl benzoate.

[0213] As the monomer (B2), at least one, preferably at least two nitrogen-containing monomers are 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; the vinyl lactam is more preferably 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; the vinyl imidazole is preferably N-vinylimidazole, 2-methyl-1-imidazole, more preferably N-vinylimidazole.

[0214] Preferably, at least two monomers (B2) are used as (B2a) and (B2b), wherein

[0215] (B2a) is at least one monomer selected from vinyl imidazole-monomers, preferably N-vinylimidazole, 2-methyl-1-imidazole, more preferably N-vinylimidazole; and

[0216] (B2b) is at least one monomer selected from vinyl lactam monomers, more preferably 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.

[0217] An additional monomer (B3) can be used as an optional monomer, such monomers being different from (B1) and (B2) and being present only 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 and not intentionally added for polymerization.

[0218] The (B3) monomer can in principle be any monomer copolymerizable with (B1) and (B2), preferably at least one monomer of 1-vinyl oxazolidone and other vinyl oxazolidones, 4-vinyl pyridine-N-oxide, N-vinyl formamide and its amines (if hydrolyzed after polymerization), N-vinyl acetamide, N-vinyl-N-methyl acetamide, alkyl esters of (meth)acrylic acid.

[0219] More preferably, (B3) is present only in an amount of less than 2% of the total amount of monomers preferably used to obtain the polymer side chain (B), and preferably is present only as an impurity and not intentionally added for polymerization, and most preferably is not present at all.

[0220] In addition to monomers (B1), (B2) and (B3), at least one additional monomer (different from the previous ones) can optionally be present for copolymerization to produce the side chain (B), wherein such additional monomer is present only in an amount of less than 2% of the total amount of monomers preferably used to obtain the polymer side chain (B), and preferably is present only as an impurity and not intentionally added for polymerization, and most preferably is not present at all.

[0221] The amounts of monomers in the graft polymer are preferably as follows:

[0222] The amount of (B) is 10% to 40%, more preferably 15% to 35% and most preferably 15% to 30%;

[0223] Based on the weight percentage of the total weight of the graft polymer, (B1) (vinyl ester) is

[0224] 0% to 20%, preferably up to 15%, more preferably up to 10%, even more preferably up to 5%;

[0225] Based on the weight percentage of the total weight of the graft polymer, (B2) (nitrogen-containing monomer) is

[0226] 10% to 40%, preferably up to 35%, more preferably up to 30%, even more preferably up to 25% and most preferably up to 20% and more preferably at least 15%,

[0227] and - more preferably -

[0228] (B2a) The amount of vinylimidazole - monomer, preferably N - vinylimidazole, is 20% to 80%, preferably 30% to 70%, most preferably 40% to 60%, each based on the weight percentage of the total weight of (B2); and

[0229] (B2b) The amount of vinyl lactam - monomer, preferably N - vinylpyrrolidone, is equal to [(the total amount of (B2) minus (B2a))];

[0230] and further provided that (B3) (additional monomer) is 0 wt.% to 5 wt.%, preferably at most 2 wt.%, more preferably at most 1 wt.%, even more preferably about 0 wt.%, based on the total weight of the graft polymer, but in all cases at most 10 wt.% of the amount of (B2).

[0231] The amount of additional monomers other than (B1), (B2), and (B3) is as detailed previously.

[0232] In a more preferred embodiment, the monomers in the graft polymer are as follows:

[0233] (B) is 15% to 30% based on the total weight of the graft polymer; and these monomers:

[0234] (B1) (vinyl ester) is absent

[0235] (B2) (nitrogen - containing monomer) is 15% to 30% based on the total weight of the graft polymer

[0236] (B2a) N - vinylimidazole, is 40% to 60% in terms of the weight percentage based on the total weight of (B2); and

[0237] (B2b) N - vinylpyrrolidone, is equal to [(the total amount of (B2) minus (B2a))];

[0238] (B3) and additional monomers are substantially absent.

[0239] In a more preferred alternative embodiment of the previous embodiment, the monomers in the graft polymer are as follows:

[0240] (B) is 15% to 30%; and these monomers:

[0241] (B1) Vinyl acetate is 5% to 10% in terms of the weight percentage based on the total weight of the graft polymer;

[0242] (B2) (nitrogen-containing monomer), based on the total weight of the graft polymer, is 10% to 25% by weight, where

[0243] (B2a) N-vinylimidazole is 40% to 60% by weight based on the total weight of (B2); and

[0244] (B2b) vinyl lactam - monomer, preferably N-vinylpyrrolidone, is equal to [(total amount of (B2) minus (B2a))];

[0245] (B3) and additional monomers are substantially absent.

[0246] In an alternative embodiment, in addition to at least one monomer (B1), at least one vinylimidazole, preferably N-vinylimidazole, is present as monomer (B2a), where monomer (B1) preferably contains vinyl acetate and even more preferably is only vinyl acetate. Even more preferably, vinyl acetate is the only monomer (B1) and N-vinylimidazole is the only monomer (B2).

[0247] In another embodiment, monomer (B1) can be partially or completely hydrolyzed after the polymerization reaction. In its preferred embodiment, monomer (B1) is partially hydrolyzed, and even more preferably hydrolyzed up to 80, 70, or 60, 50, 40, 30, 20, or 10 mole percent based on the total amount of monomer (B1). In a more preferred embodiment, the vinyl ester is not hydrolyzed at all.

[0248] It should be understood that the amounts of (A), (B), (B1), (B2), (B2a), (B2b), (B3), and additional monomers other than the previous monomers can be selected from 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 numerically, however such combined ranges for, for example, (A), (B), (B1), (B2), (B2a), (B2b), and (B3) are explicitly intended to be covered in the present invention.

[0249] 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 another 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) / (B2a) / (B2b) / (B3) and any other possible combinations.

[0250] Preferably, for all the choices that can be made for (A) / (B) and (B1) / (B2) / (B2a) / (B2b) / (B3), the same choice 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.

[0251] The graft polymers of the present invention as detailed previously have 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 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)).

[0252] M w and M n The corresponding values of and can be determined using GPC standard methods (such as the methods referenced in the experimental section). However, the molecular weight of the backbone used in the present invention can also be calculated because those reactions proceed essentially 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.

[0253] The graft polymers of the present invention can contain a certain amount of ungrafted polymer ("ungrafted side chains"), which are made from monomers that have not reacted with the polymer backbone (i.e., grafted (onto the polymer backbone) to the polymer backbone).

[0254] 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 a reduction can be achieved by suitable reaction conditions, such as the dosage of monomers and free radical initiators and their relative amounts, 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 detailed hereinbelow for the present invention in the description of the method for obtaining the graft polymers of the present invention.

[0255] It has been found that the graft polymers of the present invention, as detailed previously herein, exhibit 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.

[0256] The ratio of (A) to (B) for the examples herein is:

[0257] (A) 20% to 95%, preferably 50% to 90%, more preferably 60% to 90%, even more preferably 65% to 85%, most preferably 70% to 85% of the polymer backbone as the graft matrix, and

[0258] (B) 5% to 80%, preferably 10% to 50%, more preferably 10% to 40%, even more preferably 15% to 35% and most preferably 15% to 30% of the polymer side chain (B) grafted onto the polymer backbone (A),

[0259] wherein each percentage is based on the total weight of the graft polymer, and the sum of (A) plus (B) is 100 wt.%.

[0260] The subunits (a1), (a2), the polymer backbones (A), (A1), (A2), (A3) and (A4) as the graft matrix as defined by their structure or their preparation, and the monomers (B), (B1), (B2), (B2a), (B2b), (B3), and any one and each of the additional monomers other than (B1), (B2), (B2a), (B2b), (B3) are those as defined herein and specifically those defined previously in all its embodiments, preferred embodiments, etc. and in the examples; for the subunits (a1), (a2), the polymer backbones (A), (A1), (A2), (A3) and (A4) as the graft matrix as defined by their structure or their preparation, and the monomers (B), (B1), (B2), (B3), and any such embodiments of the additional monomers other than (B1), (B2), (B2a), (B2b), (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)).

[0261] Thus, in a preferred embodiment of the present invention, the graft polymer is characterized in that:

[0262] (A) 20% to 95%, preferably 50% to 90%, more preferably 60% to 90%, even more preferably 65% to 85%, most preferably 70% to 85% of the polymer backbone as the grafting matrix,

[0263] The polymer backbone comprises at least one subunit (a1) and at least one subunit (a2), wherein

[0264] (a1) is a unit (preferably consisting essentially of) comprising a moiety 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,

[0265] (a2) is a unit (preferably consisting of) comprising a moiety 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 consisting of at least one type of lactone and / or at least one type of hydroxy acid,

[0266] Wherein preferably the at least one lactone and / or hydroxy acid is selected from group i) and / or ii), wherein

[0267] 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;

[0268] And

[0269] 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;

[0270] Preferably lactic acid or caprolactone, more preferably caprolactone,

[0271] Wherein the polymer backbone

[0272] a) is obtained by

[0273] (A1) Copolymerization of at least one subunit (a1) and at least one subunit (a2), wherein 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);

[0274] (A2) First oligomerize / polymerize the subunit (a2), and then polymerize the product with the subunit (a1);

[0275] (A3) First oligomerize / polymerize the subunit (a1), and then copolymerize the product with the subunit (a2); or

[0276] (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, 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 a portion 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)}];

[0277] wherein 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 employed oligomer or polymer, and wherein in the case where more than one subunit (a1) and / or more than one subunit (a2) are present for polymerization, those subunits (and optionally the oligomer / polymer (if employed)) can be arranged in any order within the resulting main chain;

[0278] and wherein in the cases of (A1), (A2), and (A3), the use of a starting molecule is optional;

[0279] or

[0280] b) selected from

[0281] (A1) A main chain composed of monomers, oligomers, and / or polymers of (a1)-subunits and monomers, oligomers, and / or polymers of (a2)-subunits in a random arrangement order, where there are more than one subunit (a1) and / or more than one subunit (a2);

[0282] (A2) A main chain composed of an oligomeric or polymeric subunit (a2) as the 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.;

[0283] (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

[0284] (A4) A main chain composed of:

[0285] A first block, which has

[0286] (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

[0287] (ii) Oligomeric or polymeric subunit (a1); and

[0288] A second block, which is 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, and the second block is 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 subunits (A1) and (a2) can also be in any order, including a random structure,

[0289] 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)]

[0290] Or when using subunits (a1) and (a2) for the second block, it has the following as the idealized structure:

[0291] [End group]-[Subunit (a1)]-[Random-{Subunit (a2)-Subunit (a1)}];

[0292] And in the case of (A1), (A2) and (A3), the use of the starting molecule is optional;

[0293] And

[0294] (B) 5% to 80%, preferably 10% to 50%, more preferably 10% to 40%, even more preferably 15% to 35% and most preferably 15% to 30% of the polymer side chains (B) grafted onto the polymer backbone (A), where the polymer side chains (B) are obtainable by (co)polymerization of:

[0295] (B1) Optionally 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;

[0296] (B2) At least one, preferably at least two nitrogen-containing monomers 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, the vinyl lactam being more preferably 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 being preferably N-vinylimidazole, 2-methyl-1-imidazole, more preferably N-vinylimidazole;

[0297] Optionally

[0298] (B3) At least one further monomer, such as any one or more of 1-vinyl oxazolidinone and other vinyl oxazolidinones, 4-vinylpyridine-N-oxide, N-vinylformamide and its amine (if hydrolyzed after polymerization), N-vinylacetamide, N-vinyl-N-methylacetamide, alkyl esters of (meth)acrylic acid; and

[0299] Optionally

[0300] at least one further monomer, which is different from the previous ones, which further 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 the polymerization, where all percentages are by weight relative to the total weight of the graft polymer,

[0301] and where the amount of monomers is

[0302] in % by weight based on the total weight of the graft polymer, (B1) (vinyl ester) is

[0303] 0% to 20%, preferably up to 15%, more preferably up to 10%, even more preferably up to 5%;

[0304] in % by weight based on the total weight of the graft polymer, (B2) (nitrogen-containing monomer) is

[0305] 10% to 40%, preferably up to 35%, more preferably up to 30%, even more preferably up to 25% and most preferably up to 20% and more preferably at least 15%,

[0306] and - more preferably -

[0307] (B2a) the amount of vinylimidazole - monomer, preferably N - vinylimidazole, is 20% to 80%, preferably 30% to 70%, most preferably 40% to 60%, each in % by weight based on the total weight of (B2); and

[0308] (B2b) the vinyl lactam - monomer, preferably N - vinylpyrrolidone, is equal to [(total amount of (B2) minus (B2a))];

[0309] and further provided that (B3) (further monomer) is 0 wt.% to 5 wt.%, preferably at most 2 wt.%, more preferably at most 1 wt.%, even more preferably about 0 wt.%, but in all cases at most 10 wt.% of the amount of (B2), based on the total weight of the graft polymer.

[0310] In a more preferred embodiment, the graft polymer according to the invention and / or as detailed previously consists of:

[0311] (A) at least one polymer backbone as the graft matrix, such graft matrix being any of the polymer backbones defined previously in any of the embodiments, preferably any one of (a1), (A2), (A3) and (A4) as defined previously,

[0312] in the amounts defined in any of the embodiments herein,

[0313] Comprising a description, examples and claims,

[0314] and

[0315] (B) a polymer side chain (B) grafted onto a polymer backbone (A), wherein the polymer side chain (B) is obtainable by (co)polymerization of optionally at least one vinyl ester monomer (B1), at least one, preferably at least two nitrogen-containing monomers (B2), preferably at least one (B2a) and optionally also at least one (B2b), and optionally further monomers (B3) and optionally additional monomers other than (B1), (B2) and (B3),

[0316] All such monomers are any monomers as defined in any of the examples herein,

[0317] in amounts as defined in any of the examples herein,

[0318] Comprising a description, examples and claims.

[0319] In one embodiment of the previous embodiment, the vinyl ester monomer is vinyl acetate as the sole monomer (B1), and more preferably N-vinylimidazole is the sole monomer (B2a), and vinyl pyrrolidone is the sole monomer (B2b), and most preferably there are no other monomers (B3) and additional monomers other than the previous monomers, while in an alternative embodiment of the previous embodiment, there is no vinyl ester monomer, and N-vinylimidazole is the sole monomer (B2a), and vinyl pyrrolidone is the sole monomer (B2b), and most preferably there are no other monomers (B3) and additional monomers other than the previous monomers.

[0320] The polymers of the invention preferably have at least one, preferably two or more of the following additional properties, to be more successfully used in various application fields for the invention:

[0321] i) The polymer backbone (A) may carry two hydroxyl groups as end groups or may be capped at both ends with C1 to C22-alkyl, preferably C1 to C4 alkyl;

[0322] 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]);

[0323] iii) The biodegradability of the graft polymer is at least 35%, more preferably at least 40%, even more preferably at least 45%, and even further more preferably at least 50%, such as 46%, 47%, 48%, 49%, 50%, 55%, 60%, 65%, 70%, 75%, etc. and any value therebetween and up to 100% when tested according to OECD 301F for 28 days.

[0324] In addition, the graft polymer is preferably water-soluble to some extent to enable the use of these polymers in an aqueous environment typically present in various application fields such as those commonly targeted for the present invention. Preferably, the polymers of the present invention should exhibit medium to good, more preferably good solubility in the environment of an aqueous formulation, such as in the environment typically employed in such fields for various formulations (e.g., fabric cleaning and fabric care formulations, etc.).

[0325] Furthermore, the graft polymer solution preferably has a viscosity such that the solid concentration of the polymer is quite high for handling during and after production and for providing to the user, and the polymer can be dissolved, for example, as a "pure" (then typically liquid) product in a solvent, typically an aqueous solution containing water and an organic solvent, only water, or only an organic solvent, 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 about 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 solvent added, the viscosity is lower when the amount of 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 below 3000 mPas, more preferably 3250, or even below 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.

[0326] Of course, as a further criterion, the individual properties of a particular polymer need to be evaluated and thus each individual formulation graded for a particular field of application. Due to the wide 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 for the field of home care and in particular fabric care is of course the performance during dye transfer inhibition, for example subjecting a certain coloured fabric material to a defined washing procedure.

[0327] These examples give some guidance for the application of fabric washing, i.e. the general field of fabric care.

[0328] Depending on the individual requirements for polymers exhibiting defined degrees of biodegradability, water solubility and viscosity (i.e. handling 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.

[0329] Use

[0330] The present invention also encompasses a method for obtaining a graft polymer according to any of the previous embodiments as defined herein and in particular in the previous part but also in any of the examples disclosed herein, which method comprises the steps of polymerizing optionally at least one vinyl ester monomer (B1), at least one, preferably at least two nitrogen-containing monomers (B2), and optionally further monomers (B3) and further optionally additional monomers included as impurities in (B1), (B2) and / or (B3) in the presence of at least one polymer backbone (A), wherein these polymer side chains (B) are obtained by free radical polymerization, preferably initiated by a free radical forming compound.

[0331] wherein each of (B1), (B2), (B2a), (B2b) and (B3) (and additional monomers other than (B1), (B2), (B2a), (B2b) and (B3)) and (A), (A1), (A2), (A3) and (A4) are as defined hereinbefore in including the claims and in any of the embodiments exemplified in the following examples, where 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.

[0332] It must be noted that the "grafting method" itself, in which a polymer backbone, such as the polymer backbone (A) described above herein, is grafted with polymer side chains, is known to those skilled in the art. Any method known to the skilled person in this regard can in principle be used in the present invention.

[0333] Free radical polymerization itself is also known to the skilled person. This person also knows that the method of the present invention can be carried out in the presence of a free radical forming initiator (C) and / or at least one solvent (D).

[0334] The skilled person knows the appropriate corresponding components themselves.

[0335] 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 to the skilled person respectively.

[0336] In a preferred embodiment, the method for producing the graft polymer of the present invention and / or as detailed previously comprises polymerizing monomer (B) in the presence of at least one polymer backbone (A), preferably selected from backbones (A1), (A2), (A3) and (A4), a free 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 fraction of unreacted graft monomers (B1), (B2) and optionally (B3) and the initiator (C) in the reaction mixture remains continuously quantitatively insufficient relative to the polymer backbone (A), where additional monomers are typically not monitored as being present only as low (and thus negligible amounts) of impurities.

[0337] Generally, the amount of additional monomers other than (B1), (B2) and (B3) is minimized, preferably they are not present at all.

[0338] In an alternative embodiment, monomer (B1) is not used. In a more preferred embodiment, neither monomer (B1) nor monomer (B3) is used.

[0339] In a preferred embodiment of the method as detailed herein - when using (B1) - 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 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).

[0340] 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:

[0341] In this method, the amounts used for this method are as follows:

[0342] (A) is 20% to 95%, preferably 50% to 90%, more preferably 60% to 90%, even more preferably 65% to 85%, most preferably 70% to 85% of the polymer backbone as the grafting matrix,

[0343] (B) is 5% to 80%, preferably 10% to 50%, more preferably 10% to 40%, even more preferably 15% to 35% and most preferably 15% to 30%; wherein

[0344] in weight percent based on the total weight of the graft polymer, (B1) (vinyl ester) is

[0345] 0% to 20%, preferably up to 15%, more preferably up to 10%, even more preferably up to 5%;

[0346] in weight percent based on the total weight of the graft polymer, (B2) (nitrogen-containing monomer) is

[0347] 10% to 40%, preferably up to 35%, more preferably up to 30%, even more preferably up to 25% and most preferably up to 20% and more preferably at least 15%,

[0348] and - more preferably -

[0349] (B2a) the amount of vinylimidazole - monomer, preferably N-vinylimidazole, is 20% to 80%, preferably 30% to 70%, most preferably 40% to 60%, each in weight percent based on the total weight of (B2); and

[0350] (B2b) Vinyl lactam - monomers, preferably N - vinylpyrrolidone, is equal to [(total amount of (B2) minus (B2a))];

[0351] And further provided that (B3) (additional monomers) is 0 wt.% to 5 wt.%, preferably at most 2 wt.%, more preferably at most 1 wt.%, even more preferably about 0 wt.%, but in all cases at most 10 wt.% of the amount of (B2), based on the total weight of the graft polymer.

[0352] 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), where such additional monomer is present only in an amount of less than 2% of the total amount of monomers used to obtain polymer side chain (B), and preferably is used only as - practically inevitable - impurities rather than being intentionally added for polymerization, and most preferably is not present at all.

[0353] Preferably, the optional additional monomer (B3) is also present only as an impurity rather than being 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) is substantially absent, and most preferably even no other monomers are present except monomer (B1) and optional monomer (B2). This also applies to additional monomers other than (B1), (B2), and (B3).

[0354] In each case based on polymer side chain (B), the amount of the (radical - forming) initiator (C) is preferably 0.1% to 5% by weight, especially 0.3% to 3.5% by weight.

[0355] 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) and (B2b) - if present - more preferably (B1) and (B2), even more preferably (B1), (B2), and (B3) are present only constantly in 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.

[0356] However, in order to ensure safe temperature control - especially when the polymerization starts and / or proceeds in a large amount at high solid concentrations or from a large amount of monomers present from the start - 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 accomplished by internal or external coolers (such as heat exchangers), or by using a reflux condenser when the solvent is at its boiling temperature or when the solvent mixture is operating at a given temperature / pressure combination.

[0357] The same measures can of course be used for the preferred embodiments mentioned above, where the monomers are added over an extended period of time and thus the monomer concentration in the reaction volume remains low over time.

[0358] However, under such conditions, temperature control is usually not a key point, since the temperature is also at least partially 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 to the surface of the polymerization mixture becomes very large, such additional cooling as described above may be necessary for both variants - batch reaction or bulk reaction with a large amount of monomers present from the start, or semi - continuous or continuous polymerization reactions with typically constantly low monomer concentrations.

[0359] However, this is well - known to those skilled in the art of commercial - scale polymerization and can thus be adapted to these requirements.

[0360] According to the invention, the initiator (C) and the graft monomers (B) and especially (B1) and / or (B2) and / or (B3) (preferably with the "and" twice) - if used - are advantageously added in such a way that a low and substantially constant concentration of undissociated initiator and graft monomers (B) and especially a constant but low amount of (B1) and especially even more of (B2) (especially in the case when vinylpyrrolidone is chosen as (B2)) are present in the reaction mixture. Based on the total amount of initiator metered during monomer addition, the proportion of undissociated initiator in the entire reaction mixture is preferably ≤ 15% by weight, especially ≤ 10% by weight.

[0361] 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.

[0362] The term "average polymerization temperature" is hereby intended to mean that, although the process is essentially isothermal, due to the exothermic nature of the reaction, temperature variations may occur, which are preferably kept within the range of + / - 10 °C, more preferably within the range of + / - 5 °C.

[0363] According to the invention, the initiator (C) (for free radical formation) 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.

[0364] 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:

[0365] - tert-C4-C 12 - alkyl hydroperoxides and tert-(C9-C 12 - aralkyl) 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 peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, tert-amyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxypivalate, cumyl peroxypivalate, tert-butyl peroxybenzoate, tert-amyl peroxybenzoate and di-tert-butyl diperoxyphthalate;

[0366] - 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;

[0367] - 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;

[0368] - tert-C4-C5-alkyl peroxy (C4-C 12 - alkyl) carbonate such as tert-amyl peroxy(2-ethylhexyl) carbonate;

[0369] - di(C2-C12 -alkyl) esters such as di(n-butyl) peroxydicarbonate and di(2-ethylhexyl) peroxydicarbonate.

[0370] Depending on the average polymerization temperature, examples of particularly suitable initiators (C) are:

[0371] - At an average polymerization temperature of 50 °C to 60 °C:

[0372] 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;

[0373] - At an average polymerization temperature of 60 °C to 70 °C:

[0374] tert-butyl peroxyneopentanoate, tert-butyl peroxyneoheptanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxyneopentanoate and bis(2,4-dichlorobenzoyl) peroxide;

[0375] - At an average polymerization temperature of 70 °C to 80 °C:

[0376] 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;

[0377] - At an average polymerization temperature of 80 °C to 90 °C:

[0378] 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;

[0379] - At an average polymerization temperature of 90 °C to 100 °C:

[0380] tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl monoperoxymaleate, tert-amyl peroxy-2-ethylhexanoate, benzoyl peroxide and bis(4-methylbenzoyl) peroxide;

[0381] - At an average polymerization temperature of 100 °C to 110 °C:

[0382] tert-butyl monoperoxymaleate, tert-butyl peroxyisobutyrate and tert-amyl peroxy(2-ethylhexyl) carbonate;

[0383] - at an average polymerization temperature of 110 °C to 120 °C:

[0384] tert-butyl monoperoxy maleate, tert-butyl peroxy-3,5,5-trimethylhexanoate and tert-amyl peroxy(2-ethylhexyl) carbonate.

[0385] The preferred initiator (C) is an O-C4-C of tert-C4-C5-alkyl hydroperoxide 12 - acyl derivative, and particularly preferred are tert-butyl peroxyneodecanoate and tert-butyl peroxy-2-ethylhexanoate.

[0386] 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 60 °C to 80 °C, and in the case of using tert-butyl peroxy-2-ethylhexanoate, it is 80 °C to 100 °C.

[0387] 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. Preferably, a water-soluble or water-miscible organic solvent is used. However, water as the sole solvent is also possible in principle, but it is not preferred.

[0388] 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 1% to 40% by weight, preferably 1% to 35% by weight, more preferably 1.5% to 30% by weight, and most preferably 2% to 25% by weight.

[0389] Examples of suitable solvents (D) include:

[0390] - 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;

[0391] - 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;

[0392] - 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;

[0393] -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;

[0394] -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;

[0395] -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;

[0396] -aliphatic ketones preferably having 3 to 10 carbon atoms, such as acetone, methyl ethyl ketone, diethyl ketone and cyclohexanone;

[0397] -cyclic ethers, especially tetrahydrofuran.

[0398] The solvent (D) is advantageously those solvents which are also used for formulating the graft polymers of the present invention for use (e.g. in washing and cleaning compositions) and can thus remain in the polymerization product.

[0399] Preferred examples of these solvents are polyethylene glycols having 2-15 ethylene glycol units, polypropylene glycols having 2-6 propylene glycol units and especially alkoxylation products of C6-C8-alcohols (alkylene glycol monoalkyl ethers and polyalkylene glycol monoalkyl ethers).

[0400] Particular preference is given here to considering C8-C with a high degree of branching 16- Alkoxylation products of alcohols, which allow the preparation 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.

[0401] In an alternative embodiment, polymerization is carried out using a mixture of at least one organic solvent and water.

[0402] In a preferred embodiment, the amount of water during polymerization is low, preferably at most 10 wt.%, more preferably at most 5 wt%, even more preferably at most 1% based on the total solvent.

[0403] In a further alternative embodiment, water is used as (D) for polymerization. However, water as the sole solvent is not preferred.

[0404] The radical initiator (C) is preferably used in the form of a concentrated solution in one of the previously mentioned solvents. Of course, the concentration depends on the solubility of the radical initiator. Preferably, the concentration is as high as possible to allow as little organic solvent as possible to be introduced 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.

[0405] Preferably, the amount of water during 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 polymerization) or based on the total weight of (A) and (B) (at the start of polymerization).

[0406] 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.

[0407] 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.

[0408] 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 a vessel, but also include tubular reactors, reactor cascades from vessels or various tubes, etc.

[0409] 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 up to 15% by weight of the graft monomer (B), initiator (C) and solvent (D) 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.

[0410] In the case of a particularly preferred, substantially solvent-free process variant, initially the entire amount of 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, and the temperature is controlled such that the selected polymerization temperature is maintained on average within a range of especially + / -10 °C, particularly + / -5 °C during the polymerization.

[0411] In a further particularly preferred low-solvent process variant, except that the solvent (D) is metered in during the polymerization in order to limit the viscosity of the reaction mixture, the procedure is as described above. It is also possible to start by metering in the solvent only at a later time by advanced polymerization or to add it batchwise.

[0412] 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.

[0413] 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), where the 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 radical initiators and / or different solvents can also be used.

[0414] The temperature of the post-polymerization method step can be the same as the temperature in the main polymerization reaction (which is preferred in the present invention) or can be increased. In the case of an increase, it can typically be about 5 °C to 40 °C higher, preferably 10 °C to 20 °C.

[0415] A certain period of time can be waited between the post-polymerization and the main polymerization, where the main polymerization reaction continues, and then the post-polymerization reaction is started by starting to add an additional radical initiator.

[0416] 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 under reduced pressure or by stripping with a gas such as steam or nitrogen (such as stripping with steam made from water), preferably by vacuum distillation, while higher-boiling solvents will generally remain in the polymer product obtained.

[0417] 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 thus 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 radical initiator, unless such solvents also form part of the formulation in which the graft polymer will be used.

[0418] 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"), such as polyvinyl acetate in the case of using only vinyl acetate, and / or - when additional monomers are used - homopolymers and copolymers of vinyl esters with 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 is 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.

[0419] 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.

[0420] It is believed that the conditions considered favorable herein promote - presumably - a higher degree of grafting; such a higher degree of grafting is associated with better properties. However, this presumably higher degree of grafting does not impair biodegradation - which is attributed to the ester bonds in the main chain, which can "compensate" for the lower biodegradation of graft polymers with a higher degree of grafting - as seen in "conventional graft polymers" based on polyalkylene oxides as the main chain.

[0421] The drawback is that it is extremely difficult, if not impossible, to actually verify such a degree of grafting 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.

[0422] In another - alternative - embodiment of the present invention, after the polymerization reaction and thus after obtaining such a graft polymer, based on the total molar amount of (B1) employed, the units in the polymer side chains (B) of the graft polymer according to the present invention - if monomer (B1) is used for the method - 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%. This means that the complete or at least partial hydrolysis of the polymer side chains (B1) of the graft polymer is carried out in an additional method step after the completion of the polymerization process of the polymer side chains (B1) (including after an optional post - polymerization step, if used).

[0423] In another alternative embodiment, after the polymerization of the polymer side chain (B1) is completed, hydrolysis is not carried out on the graft polymer.

[0424] Due to this complete or at least partial hydrolysis of the units in the polymer side chain (B) of the graft polymer according to the invention derived from (B1), the corresponding side chain units derived from at least one vinyl ester monomer (B1) are changed from the corresponding ester functional group to an alcohol functional group in the polymer side chain (B). It must be noted that due to the stability aspect of "vinyl alcohol" - monomers, the corresponding vinyl alcohol is not suitable as a monomer during the polymerization of the polymer side chain (B). In order to obtain an alcohol functional group (hydroxyl substituent) in the polymer side chain (B) of the graft polymer according to the invention, the alcohol functional group is typically introduced by hydrolyzing the ester functional group of the side chain.

[0425] From a theoretical perspective, 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").

[0426] Hydrolysis can be carried out by any method known to those skilled in the art. For example, 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.

[0427] In one embodiment, vinyl acetate is used as monomer (B1), vinyl imidazole as monomer (B2a) and vinyl pyrrolidone as monomer (B2b) and no other monomers are used except (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) employed.

[0428] The graft polymer according to the invention, i.e. the polymer solution obtained from the process, can also be subjected to means of concentration and / or drying.

[0429] 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 previously disclosed, where 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.

[0430] The graft polymer solution can also be further concentrated or dried after the main polymerization and / or optional post-polymerization step and optional purification step 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 a 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.

[0431] Thus, 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.

[0432] More preferably, the process as detailed in any of the embodiments defined herein includes at least one additional process step selected from i) and ii):

[0433] i) A post-polymerization process step which is carried out after the main polymerization reaction, where an additional amount of initiator (optionally dissolved in a solvent) is preferably added over a period of 0.5 hours and up to 3 hours, preferably about 1 to 2 hours, more preferably about 1 hour, where 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 is allowed to continue, and then the post-polymerization reaction is started by beginning to add additional free radical initiator, such period of time being 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 increase preferably being about 5°C to 40°C higher, preferably 10°C to 20°C higher;

[0434] 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 a portion or substantially all of the remaining solvent (as long as they are removable due to their boiling points) and / or volatiles such as residual monomers, where

[0435] a. 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, and is carried out until the desired solid content and optionally also purity are obtained, preferably until the desired portion or all of the volatile components such as volatile solvents and / or unreacted volatile monomers are removed;

[0436] b. 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 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.

[0437] Definition

[0438] 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:

[0439] All compared with 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.

[0440] Typical applications are:

[0441] Technical applications: Such compositions and formulations include gums for any kind of non - aqueous and - preferably - water - based liquid or solid formulations, and are used as dispersants in any kind of dispersions, such as in oilfield applications, automotive applications, typically in applications where solids or liquids are to be dispersed in another liquid or solid.

[0442] Paint, varnish and colorant formulations: Such compositions and formulations include non - aqueous and - preferably - water - based paints and colorants, varnishes, finishes.

[0443] Agricultural formulations: Such compositions and formulations include formulations and compositions containing agrochemical active substances in liquid, semi-solid, mixed liquid-solid or solid environments.

[0444] Aroma chemical formulations: Such compositions and formulations include formulations in which aroma chemicals are dissolved or dispersed in liquid or solid compositions to uniformly disperse and / or maintain their stability so as to maintain their aroma characteristics over an extended period of time; also covered are compositions showing the release of aroma chemicals over time, such as delayed release or sustained release formulations.

[0445] The graft polymers of the present invention obtainable by 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.

[0446] 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.

[0447] Most preferably, the graft polymers of the present invention can be used as dye transfer inhibitors, and this is preferably for such use.

[0448] Accordingly, another subject of the present invention is the use of the graft polymers of the present invention and / or obtained by the methods of the present invention and / or obtainable and / or as detailed above in cleaning compositions, fabrics and home care products, particularly in cleaning compositions for improving the removal of oily and fatty stains, the removal of solid dirt such as clay, the prevention of graying on the fabric surface, scale inhibitors, and / or as a dye transfer inhibitor, preferably as a dye transfer inhibitor, wherein the cleaning composition is preferably a laundry detergent formulation, more preferably a liquid laundry detergent formulation.

[0449] 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 aforementioned applications in this chapter: such as in fabric care and home 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, in textile and leather treatment products for use during or after production, in formulations containing inorganic salts such as especially silver salts, in mining, metal production and treatment (including metal refining and metal hardening), in the purification of liquids such as industrial, production or consumer waste water, preferably in agrochemical compositions and cleaning compositions and in fabric and home care products, especially in cleaning compositions for improved removal of oily and fatty stains, removal of solid dirt such as clay, prevention of graying of fabric surfaces, scale inhibitors and / or as dye transfer inhibitors, 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.

[0450] Accordingly, another subject of the present invention is also a cleaning composition, a fabric care and home care product, an industrial and institutional cleaning product, an agrochemical formulation, or a formulation or product for any of the applications and application areas mentioned previously, preferably in laundry detergents, in cleaning compositions and / or in fabric and home care products, each comprising at least one graft polymer as defined above or obtained or obtainable by the process of the present invention and / or as detailed herein.

[0451] 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 a fabric care and home care product, an industrial and institutional cleaning product, or a formulation or product for any of the applications mentioned previously, preferably in a cleaning composition and in fabric treatment agents, fabric care products and laundry 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 dye transfer inhibition.

[0452] Uses of the present invention and the compositions / products of the present invention cover the 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.

[0453] Laundry detergents, cleaning compositions and / or fabric and home care products are known per se to those skilled in the art. Any compositions etc. known to those skilled in the art in relation to the corresponding uses can be used in the context of the present invention.

[0454] 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 dye transfer inhibition, preferably a laundry detergent formulation, more preferably a liquid laundry detergent formulation.

[0455] The graft polymer can also support 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 improve the washing and cleaning performance of the formulation.

[0456] In one embodiment, it is also 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, mannanases and peroxidases (oxicoreductase), dispersin, and combinations of at least two of the foregoing types, preferably at least one enzyme is selected from lipases.

[0457] Accordingly, another subject of the present invention is a cleaning composition, such as a fabric and home care product and an industrial and institutional (I&I) cleaning product, which comprises at least one graft polymer as defined above, and in particular a cleaning composition for improved dye transfer inhibition.

[0458] At least one graft polymer as described herein is present in the cleaning composition of the present invention in an amount in the range of from about 0.01% 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 up to 2%, each based on weight % of the total weight of such composition or product; such cleaning composition may - and preferably does - further comprise from about 1% to about 70% by weight of a surfactant system.

[0459] Preferably, such 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, which comprises at least one graft polymer of the present invention and optionally further comprises at least one surfactant or surfactant system, providing improved dye transfer inhibition.

[0460] Even more preferably, the cleaning composition of the present invention which comprises at least one graft polymer of the present invention and optionally further comprises at least one surfactant or surfactant system - as detailed previously - is those for cleaning and dye transfer inhibition within clothing (such as those on fabrics), and may additionally comprise at least one enzyme selected from the list consisting of: optionally further comprises at least one enzyme, which is preferably selected from one or more of optionally further comprises 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.

[0461] In one embodiment, the graft polymer of the present invention can be used to reduce 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.

[0462] In another embodiment, the graft polymer of the present invention can be used for improved dye transfer inhibition, i.e., preventing the transfer of dyes from one piece of 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 (B2a), and even more preferably at least one vinylimidazole. Such graft polymers containing such (B2) are defined herein with suitable compositions and methods for obtaining such graft polymers.

[0463] In a preferred embodiment, the cleaning composition of the present invention is a liquid or solid laundry detergent composition.

[0464] 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.

[0465] In one embodiment, the graft polymer of the present invention can be used in a cleaning composition comprising a surfactant system that contains 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.

[0466] In a further embodiment, the graft polymer of the present invention can be used in any type of cleaning composition, such as laundry detergents, etc., which contains 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.

[0467] In a further embodiment, the graft polymer of the present invention can be used in any type of cleaning composition, such as laundry detergents, etc., which contains 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.

[0468] In one embodiment of the present invention, the graft polymer is a component of a cleaning composition, such as preferably a laundry formulation, more preferably a liquid laundry formulation, each of which additionally contains at least one surfactant, preferably at least one anionic surfactant.

[0469] In such a laundry detergent, cleaning composition or fabric and home care product 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 the amounts detailed in any such embodiment disclosed herein (including specifically any previous most preferred embodiment in this chapter disclosing such graft polymers) - in a concentration of from about 0.01% 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 based on the weight % of the total weight of such composition or product, and all values therebetween, 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, redox enzymes, 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-hydroxydiphenyl ether at a concentration of from 0.001% to 3%, preferably from 0.002% to 1%, more preferably from 0.01% to 0.6% each based on the 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.

[0470] In a further embodiment, the present invention also encompasses a composition comprising a graft polymer as described previously herein, further comprising an antimicrobial agent as disclosed hereinafter (preferably selected from the group consisting of 2-phenoxyethanol), more preferably containing the antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition; even more preferably containing 0.1% to 2% of phenoxyethanol.

[0471] In a further embodiment, the present invention also encompasses a method of preserving an aqueous composition against microbial contamination or growth, such composition comprising a graft polymer as described previously herein, such composition preferably being a detergent composition, such method comprising adding at least one antimicrobial agent selected from the antimicrobial agents disclosed hereinafter, such antimicrobial agent preferably being 2-phenoxyethanol.

[0472] 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 laundry, said composition comprising a graft polymer as described previously 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.

[0473] In a further embodiment, the present invention also encompasses a method of washing fabrics or cleaning hard surfaces, the method comprising treating the fabrics or hard surfaces with a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dish composition, even more preferably a liquid laundry detergent composition or a liquid fabric softener composition for use in laundry, said composition comprising a graft polymer as described previously herein, said composition further comprising 4,4'-dichlor-2-hydroxy-diphenyl ether.

[0474] The choice of additional surfactant in these embodiments can depend on the application and the desired benefits.

[0475] 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 are not biodegradable or exhibit much lower biodegradability.

[0476] Description of cleaning compositions, formulations and their ingredients

[0477] 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.

[0478] As used herein, the term "about" encompasses the exact numerical value "X" being referred to, such as "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".

[0479] Similarly, the ranges and values disclosed herein should not be understood 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".

[0480] The term "water-free" means that the composition contains no more than 5 wt.-% water, based on the total amount of solvent, in another embodiment no more than 1 wt.-% water, based on the total amount of solvent, and in a further embodiment the solvent contains no water at all.

[0481] The compositions disclosed herein may "comprise" the components disclosed herein (i.e., contain other ingredients), "consist essentially of the components disclosed herein" (predominantly or almost only contain the ingredients mentioned and only very small amounts of other ingredients mainly as impurities), or "consist of the components disclosed herein" (i.e., contain only the ingredients mentioned and additionally may only contain impurities that are unavoidable in the technical environment, preferably only these ingredients).

[0482] Similarly, the terms "substantially free of", "substantially free from", or "substantially not (containing / comprising)" may be used herein; this means that the indicated material is present in a very small amount that is not intentionally added to the composition to form part of it, or, preferably, is not present at an analytically detectable level. It means to include 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 may be present at a level of less than 1%, or even less than 0.1%, or even far less than 0.01%, or even 0% by weight of the composition.

[0483] 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 said corresponding method or process, where the product is not actually produced (obtained) by such method or process. However, the term "obtainable by" also includes the more restrictive term "obtained by", i.e., products actually produced (obtained) by the method or process described in the corresponding specific context.

[0484] 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.

[0485] Unless otherwise indicated, all temperatures herein are in degrees Celsius (°C). Unless otherwise specified, all measurements herein are made at 20 °C and at atmospheric pressure. In all embodiments of this disclosure, unless otherwise specifically stated, all percentages are by weight of the total composition. Unless otherwise specifically stated, all ratios are weight ratios.

[0486] 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.

[0487] The definitions given in the "- Definitions" section and their preferred options are included as part of the present invention as described herein.

[0488] This invention encompasses the specific embodiments described throughout this disclosure as part of the invention; various additional options are disclosed in the specification of the invention 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 invention.

[0489] Cleaning composition

[0490] 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.

[0491] Compositions for " Fabric care composition " 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).

[0492] The phrase " Composition 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-treatments, laundry pre-treaters, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, wash additives, post-rinse fabric treatments, ironing aids, unit dose formulations, delayed delivery formulations, detergents contained on or in porous substrates or nonwoven 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 treatments, post-wash treatments, or can be added during the rinse or wash cycle of a washing operation, and are further detailed below when describing the uses and applications of the graft polymers of the invention and compositions containing such graft polymers.

[0493] " Cleaning additive”Comprising cleaning compositions, including but 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 wash 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 wash products, most preferably liquid laundry detergent formulations or liquid laundry detergent products.

[0494] The cleaning compositions of the present invention can be in any form, namely 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; of the type delivered in single-, double-, or multi-compartment bags or containers; single-phase or multi-phase unit doses; spray or foam detergents; pre-moistened wipes (i.e., cleaning compositions combined with nonwoven materials, such as the cleaning compositions discussed in US 6,121,165, Mackey et al.); dry wipes (i.e., cleaning compositions combined with nonwoven materials, such as the cleaning compositions discussed in US 5,980,931, Fowler et al.), which are activated with water by the user or consumer; and other homogeneous, heterogeneous, single-phase or multi-phase cleaning product forms.

[0495] 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.

[0496] 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.

[0497] 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.

[0498] 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.

[0499] 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 compositions 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 compositions (especially when such compositions are used in their field of use).

[0500] 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.

[0501] All such cleaning compositions, their ingredients (including (auxiliary) cleaning additives), their general compositions and more specific compositions are known, as for example in publications 800542 and 800500 published by Protegas of Liechtenstein and also as shown in WO2022 / 136409 and WO 2022 / 136408, where in any of the foregoing prior art documents, the graft polymers within the general compositions disclosed in the foregoing 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 foregoing 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.

[0502] 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 the person 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 in a concentration of generally about 0.01% to about 20%, preferably 0.05% to 10%, more preferably about 0.1% to 8%, even more preferably about 0.2% to about 6% and further more preferably about 0.2% to about 4% and most preferably in an amount of up to 2%, each calculated as weight % relative to the total weight of such composition or product.

[0503] Laundry composition

[0504] 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.

[0505] 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 vinyl pyrrolidone), 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, pearlescents, colorants, dye transfer inhibitors, fabric softeners, carriers, foam boosters, foam inhibitors (antifoaming agents), color speckle removers, silver care agents, anti-tarnish agents and / or anti-corrosion agents, sources of alkalinity, pH regulators, pH buffers, hydrotropes, washing granules, antibacterial and antimicrobial agents, preservatives, antioxidants, softeners, carriers, fillers, solvents, processing aids, pro-perfumes and fragrances.

[0506] 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.

[0507] In addition to surfactant systems and graft polymers, liquid cleaning compositions can additionally - and preferably do - contain at least one of the following: rheology control / modifying agents, emollients, humectants, skin rejuvenating actives, and solvents.

[0508] Solid compositions can additionally - and preferably do - contain at least one of fillers, bleaches, bleach activators and catalytic materials.

[0509] Suitable examples and levels of use of such cleaning adjuncts can be found in WO 99 / 05242, U.S. Patent Nos. 5,576,282, 6,306,812B1 and 6,326,348B1.

[0510] 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 laundering benefits to soiled materials.

[0511] 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.

[0512] The surfactant system can consist of one surfactant or can 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 provide cleaning, stain removal, or washing benefits to soiled materials.

[0513] 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 can comprise a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof.

[0514] Universal cleaning compositions and formulations

[0515] 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.

[0516] Non-limiting examples of anionic surfactants useful herein - which can 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).

[0517] 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.

[0518] 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 18The sulfate half-ester of C - alkanol (ethoxylation: 1 to 50 mol of ethylene oxide / mol).

[0519] In one embodiment of the present invention, it is also possible to use an alcohol polyether sulfate derived from a branched (i.e., synthetic) C 11 -C 18 - alkanol (ethoxylation: 1 to 50 mol of ethylene oxide / mol).

[0520] Preferably, based on C 12 -C 18 - fatty alcohol or based on a branched (i.e., synthetic) C 11 -C 18 - The alkoxylation group of the two types of alkoxylated alkyl sulfates of alcohol is an ethoxylation group, and the average ethoxylation degree of any alkoxylated alkyl sulfate is 1 to 5, preferably 1 to 3.

[0521] 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 equal to or less than 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.

[0522] 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.

[0523] Nonionic surfactants - which can also be used in combination with more than one other surfactant - non - limiting examples include: C8 - C18 alkyl ethoxylates, such as those from Shell nonionic surfactants; as 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 US 4,483,780 and US 4,483,779; polyhydroxy fatty acid amides, as discussed in US 5,332,528; and ether-capped poly(oxyalkylated) alcohol surfactants, as discussed in US 6,482,994 and WO 01 / 42408.

[0524] 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, and in addition alkylphenol ethoxylates, alkyl glycosides, polyhydroxy fatty acid amides (glucamides). Examples of (additional) amphoteric surfactants are the so-called amine oxides.

[0525] Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds having the general formula (A)

[0526]

[0527] where the variables are defined as follows:

[0528] R1 is selected from straight-chain C1-C10-alkyl, preferably ethyl and particularly preferably methyl,

[0529] R2 is selected from C8-C22-alkyl, such as n-C8H17, n-C10H21, n-C12H25, n-C14H29, n-C16H33, or n-C18H37,

[0530] 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, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, or isodecyl,

[0531] m and n are in the range from 0 to 300, where the sum of n and m is at least one.

[0532] Preferably, m is in the range from 1 to 100 and n is in the range from 0 to 30.

[0533] Here, the compound of general formula (A) can be a block copolymer or a random copolymer, preferably a block copolymer.

[0534] Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of general formula (B)

[0535]

[0536] where the variables are defined as follows:

[0537] R 1 identical or different and selected from straight-chain C1-C4-alkyl, preferably the same in each case and being ethyl, and particularly preferably methyl,

[0538] 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 ,

[0539] a is a number in the range from 0 to 6, preferably from 1 to 6,

[0540] b is a number in the range from 0 to 20, preferably from 4 to 20,

[0541] d is a number in the range from 4 to 25.

[0542] Preferably, at least one of a and b is greater than zero.

[0543] Here, the compound of general formula (B) can be a block copolymer or a random copolymer, preferably a block copolymer.

[0544] Further suitable nonionic surfactants are selected from diblock and multiblock copolymers composed 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 equally suitable. An overview of suitable further nonionic surfactants can be found in EP-A 0 851 023 and DE-A 198 19 187.

[0545] Of course, mixtures of two or more different nonionic surfactants can also be present.

[0546] In a preferred embodiment of the present invention, the nonionic surfactant is selected from C12 / 14 and C16 / 18 fatty alcohol alkoxylates, C13 / 15 oxoalcohol alkoxylates, C13-alkanol alkoxylates, and 2-propylheptanol alkoxylates, each of which has 3 to 15 ethoxy units, preferably 5 to 10 ethoxy units, or has 1 to 3 propoxy units and 2 to 15 ethoxy units.

[0547] Non-limiting examples of zwitterionic surfactants - which may 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").

[0548] Preferred examples of zwitterionic 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 oxide may 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.

[0549] Preferably, the amine oxide is characterized by the following formula

[0550] R1-N(R2)(R3)-O

[0551] 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 referred to 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 approximately 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 from 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.

[0552] In a preferred embodiment of the invention, the zwitterionic surfactant is selected from C8-C18 alkyl-dimethylamine oxides and C8-C18 alkyl-bis(hydroxyethyl)amine oxides.

[0553] The cleaning composition can also contain zwitterionic surfactants - which can also be used in combination with more than one other surfactant.

[0554] Suitable zwitterionic surfactants include betaines such as alkyl betaines, alkylamido betaines, amidazolinium betaines, sultaines (INCI Sultaine), and phosphobetaines. Examples of suitable betaines and sultaines are as follows (according to INCI nomenclature): Almond amidopropylof betaine, Apricotamidopropylbetaine, Avocado oil amidopropyl betaine, Babassu oil amidopropyl betaine, Behenyl amidopropyl betaine, Behenyl betaine, Erucamidopropyl betaine, Capryloyl / Capramidopropyl betaine, Carnitine, Cetyl betaine, Cocamide ethyl betaine, Cocamide propyl betaine, Cocamide propyl hydroxysultaine, Coco betaine, Coco hydroxysultaine, Coco / Oleamide propyl betaine, Coco sultaine, Decyl betaine, Oleyl glycine dihydroxyethyl ester, Soybean 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, Milkamide propyl betaine, Mink oil amidopropyl betaine, Myristamidopropyl betaine, Myristyl betaine, Oleamide propyl betaine, Oleamide propyl hydroxysultaine, Oleyl betaine, Olive oil amidopropyl betaine, Palm oil amidopropyl betaine, Palmamidopropyl betaine, Palmitoyl carnitine, Palm kernel oil amidopropyl betaine, Polytetrafluoroethylene acetoxypropyl betaine, Castor oil amidopropyl betaine, Sesame oil amidopropyl betaine, Soybean oil amidopropyl betaine, Stearamidopropyl betaine, Stearyl betaine, Tallowamide propyl betaine, Tallowamide propyl hydroxysultaine, Tallow betaine, Tallow dihydroxyethyl betaine, Undecylenamidopropyl betaine, and Wheat germ oil amidopropyl betaine.

[0555] Preferred betaines are, for example, C 12 -C 18 -alkyl betaines and sultaines. The zwitterionic surfactant is preferably a betaine surfactant, more preferably a cocamide propyl betaine surfactant.

[0556] 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).

[0557] 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. Builders are selected from citrates, phosphates, silicates, carbonates, phosphonates, aminocarboxylates and polycarboxylates.

[0558] 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.

[0559] 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 regard 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 respective composition, determined by gravimetry.

[0560] The term carbonate includes alkali metal carbonates and alkali metal hydrogen carbonates, preferably sodium salts. Particularly preferred is Na2CO3.

[0561] Examples of phosphonates are hydroxyalkylphosphonates and aminoalkylphosphonates. Among the hydroxyalkylphosphonates, 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 aminoalkylphosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and also their higher homologues. They are preferably used in the form of neutral reaction sodium salts, such as the hexasodium salt of EDTMP or the heptasodium and octasodium salts of DTPMP.

[0562] 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, especially the sodium salts of the respective fully neutralized compounds.

[0563] In the context of the present invention, silicates particularly include disodium silicate and sodium metasilicate, aluminosilicates such as zeolites and layered silicates, especially those having the formulas α-Na2Si2O5, β-Na2Si2O5 and δ-Na2Si2O5.

[0564] 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.

[0565] 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.

[0566] Oligomeric or polymeric polycarboxylates are, for example, polyaspartic acid and its alkali metal salts, especially its sodium salt, (meth)acrylic acid homopolymers and (meth)acrylic acid copolymers and their alkali metal salts, especially their sodium salts.

[0567] Suitable comonomers are monoethylenically unsaturated dicarboxylic acids, such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid. Suitable polymers are especially 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, especially from 3000 to 8000 g / mol.w Further suitable copolymer polycarboxylates are in particular those of acrylic acid with 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.

[0568] 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.

[0569] It is also possible to use copolymers of 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) with at least one hydrophilically or hydrophobically modified comonomer as listed below.

[0570] 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 polyisobutenes having on average 12 to 100 carbon atoms / molecule.

[0571] Suitable hydrophilic comonomers are monomers having sulfonate or phosphonate groups, and also nonionic monomers having hydroxyl functional groups or epoxyalkyl groups. 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.

[0572] 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, benzenesulfonic 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.

[0573] Particularly preferred monomers containing phosphonic acid groups are vinylphosphonic acid and its salts.

[0574] 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.

[0575] In addition, amphoteric polymers can also be used as builders.

[0576] The compositions according to the invention can contain, for example, in total in the range 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 in the range 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.

[0577] 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, particularly preferably sodium. In one embodiment of the invention, the pH > 7 is adjusted by using amines, preferably alkanolamines, more preferably triethanolamine.

[0578] In one embodiment of the invention, the laundry formulations according to the invention additionally contain at least one enzyme.

[0579] 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 aforementioned types.

[0580] This one or more enzymes can be incorporated at a level sufficient to provide an effective amount for cleaning. The preferred amount is an active enzyme in the range of 0.001% to 5% by weight in the detergent composition according to the invention. An enzyme stabilization system can also be used together with the enzyme, such as calcium ions, boric acid, boronic acid, propylene glycol and short-chain carboxylic acids. In the context of the present invention, the short-chain carboxylic acids are selected from monocarboxylic acids having 1 to 3 carbon atoms / molecule and dicarboxylic acids selected from those 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.

[0581] Preferably, the at least one enzyme is a detergent enzyme.

[0582] In one embodiment, the enzyme is classified as an oxidoreductase (EC 1), transferase (EC 2), hydrolase (EC 3), lyase (EC 4), isomerase (EC 5), or ligase (EC 6). 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 enzyme is a hydrolase (EC3).

[0583] In a preferred embodiment, the enzyme is selected from the group consisting of

[0584] 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.

[0585] 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 2021032881 A1.

[0586] The composition of the present invention may contain 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.

[0587] The enzyme can be incorporated into the composition at a level sufficient to provide an effective amount for achieving beneficial effects, preferably for primary washing effects and / or secondary washing effects, such as anti-greying or anti-fuzzing effects (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.

[0588] Preferably, the enzyme-containing composition further comprises an enzyme stabilization system.

[0589] 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.

[0590] 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 of the compounds selected from the group consisting of salts, polyols, and short-chain carboxylic acids, and preferably a combination of one or more of the 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.

[0591] The composition according to the invention can comprise one or more bleaching agents (bleaching agents).

[0592] 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 peracid H2SO5 and persulfates.

[0593] In view of this, the alkali metal salts can also be alkali metal bicarbonates, alkali metal perborohydrates, and alkali metal persulfates in each case. However, in each case, the dibasic alkali metal salts are preferred.

[0594] The formulation 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 and also cobalt-, iron-, copper- and ruthenium-amine complexes may also be used as bleach catalysts.

[0595] The formulation according to the invention may comprise one or more bleach activators such as tetraacetylethylenediamine, tetraacetylmethylenediamine, tetraacetylglycoluril, tetraacetylhexamethylenediamine, 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).

[0596] The formulation 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, especially benzotriazole, bisbenzotriazole, aminotriazole, alkylaminotriazole, and also phenolic derivatives such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.

[0597] In one embodiment of the invention, the formulation according to the invention comprises in total from 0.1% to 1.5% by weight of corrosion inhibitor.

[0598] The formulation according to the invention may further comprise a cleaning polymer and / or a detergency polymer and / or an anti-greying polymer.

[0599] Additional cleaning polymers may include, but are not limited to, "polyfunctional polyethyleneimine" (e.g. HP20 from BASF) and / or "polyfunctional diamine" (e.g. HP96 from BASF). Such polyfunctional 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 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 / NH-functional group.

[0600] 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 / NH-functional group, and which preferably bears two cationic ammonium groups and two anionic sulfate groups.

[0601] Suitable additional polyfunctional polyethylenimines, polyfunctional diamines and oligamines include those claimed in WO 2021 / 254828, WO 2022 / 136408A1, WO 2022 / 136409 A1, WO 2021 / 165468, WO 2023 / 021103, WO2023 / 021104, WO 2023 / 021105 and WO 2023 / 117494.

[0602] In a preferred embodiment of the present invention, the cleaning composition may contain at least one polyfunctional polyethylenimine and / or at least one polyfunctional diamine and / or oligamine, specifically any one of the claimed polymers from WO 2021 / 254828, WO 2022 / 136408A1, WO 2022 / 136409 A1, WO 2021 / 165468, WO 2023 / 021103, WO 2023 / 021104, WO 2023 / 021105 and / or WO 2023 / 117494 to improve the cleaning performance, such as preferably improving the stain removal ability, especially the primary detergency of the laundry detergent on particulate stains on polyester fabrics. The polyfunctional polyethylenimine or polyfunctional diamine or oligamine or a mixture thereof as described above may be added to the laundry detergent and cleaning composition in an amount generally from 0.05 to 15 wt%, preferably from 0.1 to 10 wt%, more preferably from 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).

[0603] 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 polyethylenimines and polyfunctional diamines and oligamines and mixtures thereof.

[0604] 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 polyethylenimines and polyfunctional diamines and oligamines and mixtures thereof is from 10:1 to 1:10, preferably from 5:1 to 1:5 and more preferably from 3:1 to 1:3.

[0605] 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.

[0606] The laundry formulation comprising the polymer of the present invention may also contain at least one complexing agent.

[0607] Preferred complexing agents are methylglycine diacetic acid (MGDA) and glutamic acid diacetic acid (GLDA) and their salts. Particularly preferred complexing agent is 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%).

[0608] MGDA and GLDA may be present as racemates or enantiomerically pure compounds. GLDA is preferably selected from L-GLDA or an enantiomerically enriched mixture of L-GLDA, in which there is at least 80 mol%, preferably at least 90 mol% of L-GLDA.

[0609] In one embodiment of the invention, the complexing agent is racemic MGDA. In another embodiment of the invention, the complexing agent is selected from L-MGDA and the enantiomeric mixture of L- and D-MGDA, where L-MGDA is in the vast majority and where the L / D molar ratio is in the range from 55:45 to 95:5, preferably from 60:40 to 85:15. The L / D molar ratio can be determined, for example, by polarimetry or by chromatographic means, preferably by HPLC with a chiral column, for example with cyclodextrin as the stationary phase or an optically active ammonium salt immobilized on the column. For example, immobilized D-penicillamine salt can be used.

[0610] MGDA or GLDA is preferably used as a salt. Preferred salts are ammonium salts and alkali metal salts, particularly preferably the potassium salt and especially the sodium salt. These can have, for example, the following general formula (CA I) or (CA II):

[0611] [CH3-CH(COO)-N(CH2-COO)2]Na 3-x-y K x H y (CA I)

[0612] x is in the range from 0.0 to 0.5, preferably up to 0.25,

[0613] y is in the range from 0.0 to 0.5, preferably up to 0.25,

[0614] [OOC-(CH2)2-CH(COO)-N(CH2-COO)2]Na 4-x-y K x H y (CA II)

[0615] x is in the range from 0.0 to 0.5, preferably up to 0.25,

[0616] y is in the range from 0.0 to 0.5, preferably up to 0.25.

[0617] The trisodium salt of MGDA and the tetrasodium salt of GLDA are very particularly preferred.

[0618] Laundry formulations comprising the polymers of the invention can also comprise at least one antimicrobial agent.

[0619] Antimicrobial agents are chemical compounds that kill microorganisms or inhibit their growth or reproduction. Microorganisms can be bacteria, yeasts or moulds. 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.

[0620] The composition / formulation may contain one or more antimicrobial agents and / or preservatives as listed on pages 35 to 39 of the patent WO 2021 / 115912 A1 (“Formulations comprising a hydrophobically modified polyethyleneimine and one or more enzymes”).

[0621] 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:

[0622] 4,4'-dichloro-2-hydroxy diphenyl ether (other names: 5-chloro-2-(4-chlorophenoxy)phenol, hydroxy dichlorodiphenyl 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-benzenemethanol, (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; didodecyldimethylammonium chloride (“DDAC”); N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine (“diamine”); peracetic acid; hydrogen peroxide.

[0623] 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.

[0624] 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%.

[0625] The laundry formulation of the present invention can comprise at least one antimicrobial agent from the above list and / or its combination, and / or a combination with at least one other antimicrobial agent not listed herein.

[0626] The formulations according to the invention may also contain water and / or additional organic solvents, such as ethanol or propylene glycol, and / or fillers such as sodium sulfate.

[0627] Additional optional ingredients may be, but are not limited to, viscosity regulators, cationic surfactants, foam boosters or defoamers, fragrances, dyes, optical brighteners, and dye transfer inhibitors.

[0628] Liquid detergent formulation

[0629] 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 dirt that should 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 solid formulations - where the enzyme and the polymer can be separated by coating or added into separate particles that are mixed - as well as liquid and semi - liquid formulations, where the polymer and the enzyme can be separated by formulating them in different compartments (such as different compartments of a multi - compartment sachet or bottle with 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 an appropriate amount at each individual point of use. Such multi - compartment sachets and bottles, etc. are also known to the person skilled in the art.

[0630] In addition to all other ingredients mentioned, the liquid formulations disclosed in this section may also contain 0% to 2%, preferably about 1%, of 2 - phenoxyethanol.

[0631] The liquid formulations disclosed above and below may contain 0 - 0.2%, preferably about 0.15%, of 4,4’ - dichloro - 2 - hydroxy diphenyl ether, along with all other ingredients mentioned. In addition to all other ingredients mentioned, the solid laundry compositions without bleach may also contain 0% - 0.2%, preferably about 0.15%, of 4,4’ - dichloro - 2 - hydroxy diphenyl ether.

[0632] The formulations disclosed in this section may also - in addition to all 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 EP1921147B1 and having the amino acid substitution R101E (numbering according to BPN), and wherein the amylase is an amylase having at least 90% sequence identity with SEQ ID NO:54 of WO 2021032881 A1, and such enzymes are preferably present in the formulation 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.

[0633] The following compositions (including those in the tables) shown below 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.

[0634] When the compositions shown do not contain the graft polymer of the present invention, such compositions are comparative compositions. 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 compositions are considered to fall within the scope of the present invention.

[0635] In a preferred embodiment, the graft polymer according to the present invention is used in laundry detergents.

[0636] The liquid laundry detergent according to the present invention consists of:

[0637]

[0638] Up to 100% water in total.

[0639] The preferred liquid laundry detergent according to the present invention consists of:

[0640]

[0641]

[0642] Up to 100% water in total.

[0643] The solid laundry detergent (such as powder, granule or tablet) according to the present invention consists of:

[0644] The sum of these components totals 100%.

[0645] The preferred solid laundry detergent according to the present invention consists of the following:

[0646]

[0647] Up to a total of 100% water

[0648] General formulation of the laundry detergent composition according to the present invention:

[0649] (Values: wt%)

[0650]

[0651]

[0652] Liquid laundry frame formulation according to the present invention:

[0653]

[0654] Liquid laundry frame formulation according to the present invention - continued:

[0655]

[0656]

[0657] Laundry powder frame formulation according to the present invention:

[0658]

[0659]

[0660] Laundry powder frame formulation according to the present invention - continued:

[0661]

[0662] The following three tables show additional typical liquid detergent formulations LD1, LD2, and LD3: (Values: wt.% active substance) Liquid detergent 1 - LD1 "excellent" detergent;

[0663]

[0664]

[0665] Liquid detergent 2 - LD2 "medium" performance detergent

[0666] 1,2 - propylene glycol <![CDATA[Sodium alkylbenzenesulfonate (C 10 -C 13 )]]> 5.5 <![CDATA[C reacted with 7 moles of EO 13 / C 15 -oxoalkanol]]> 5.4 Ethanol 6 Potassium cocoate 2 Monoethanolamine 2.4 Lauryl ether sulfate 2.5 Sodium citrate 5.4 Sokalan HP96 3 The polymer of the present invention or the comparison 2 Graft polymer* 0.1-4 Water 0-2 Made up to 100 Liquid detergent formulation

[0667] Liquid Detergent 3-LD3 “Medium” Performance “Bio-based” Detergent

[0668] MGDA APG, branched C13 glucoside 5.5 1,2 - propylene glycol 3.5 Ethanol 6 Potassium cocoate 2 NaOH 4.4 Lauryl ether sulfate 2.2 Sodium citrate 9.5 The polymer of the present invention or the comparison 3 Graft polymer* 0.1-4 Water 0-2 Made up to 100 Example section

[0669] All three tables for LD1, LD2, LD3 previously: *“Graft polymer” = (polyethylene glycol with Mn 6000 g / mol as the graft matrix, grafted with 40 wt% vinyl acetate (based on the total polymer weight; produced according to the general disclosure of WO2007138054 A1)).

[0670] Preferably, in the respective laundry detergents, cleaning compositions, and / or fabric and household care products, each by weight percent based on the total weight of such composition or product, the at least one graft polymer is present at a concentration of about 0.01% to about 20%, preferably 0.05 to 10%, more preferably about 0.1% to 8%, even more preferably about 0.2% to about 6% and further more preferably about 0.2% to about 4%, and most preferably in an amount up to 2% (and all values therebetween and including all ranges, all such ranges being produced 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 with any one of the upper limit values mentioned and including 19, 18, 17, 16, 14, 13, 12, 11, 9, 8, 7, and 6).

[0671] The present invention encompasses the specific embodiments described throughout this disclosure as part of the present invention; the various additional options disclosed as “optional”, “preferred”, “more preferred”, “even more preferred”, or “most preferred” options for the specific embodiments in this specification 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 present invention.

[0672] The following examples should further illustrate the present invention without limiting the scope of the present invention.

[0673] Example

[0674] Polymer biodegradability

[0675] Biodegradation in wastewater was tested in triplicate using OECD 301F manometric respirometry. The test substance at 30 mg / mL was inoculated into wastewater extracted from the Mannheim wastewater treatment plant and incubated for 28 days at 25 °C in a closed flask. During this time, oxygen consumption was measured as the change in pressure inside the flask using an OxiTop C (WTW). The CO2 evolved was absorbed using NaOH solution. After blank correction, the amount of oxygen consumed by the microbial population during biodegradation of the test substance was expressed as % of ThOD (theoretical oxygen demand).

[0676] The number-average molecular weight (Mn), weight-average molecular weight (Mw), and polydispersity Mw / Mn of the graft polymers of the present 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. A DRIAgilent 1100 can be used as the detection system. Poly(ethylene glycol) (PEG) standards (PL) with a molecular weight Mn ranging from 106 to 1 378 000 g / mol can be used for calibration.

[0677] 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 of the reaction. Since those reactions proceed essentially to completion, this is an acceptable way to calculate the molecular weight.

[0678] The following main chains were prepared as the main chains of the graft polymers of the present invention; the abbreviations of their structures are:

[0679] A: 5CL + 61EO + 5CL

[0680] B: 1.5CL + 61EO + 1.5CL

[0681] C: 23EO + 4CL + neopentyl glycol + 4CL + 23EO

[0682] D: 20EO / 2PO + 4CL + neopentyl glycol + 4CL + 20EO / 2PO

[0683] E: 20EO + 1CL + neopentyl glycol + 1CL + 20EO

[0684] Abbreviations used: EO = ethylene oxide; CL = ε-caprolactam; PO = propylene oxide

[0685] Explanation of the short description:

[0686] The main chain of Example A = "5CL + 61EO + 5CL" is equivalent to

[0687] "(PEG with 61 EO) + 35 caprolactone / OH"

[0688] = First, react PEG (polyethylene glycol) prepared from an average of 61 moles of EO with 3 moles of CL (per hydroxyl end group), and then react with 35 moles of EO (per hydroxyl end group formed in the previous step).

[0689] Graft polymer - General synthesis according to method (a)

[0690] First, charge 100 g of the main chain (see Table 3) and 100 g of water into a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere and heat to 80 °C. The initiator tert-butyl peroxypivalate (amount see Table 1) is dosed as an 8.0 wt% solution in isopropanol at a constant flow rate starting for 6:30 h. At the same time, the feed of a 2.0 wt% aqueous solution of vinylimidazole, vinylpyrrolidone, and 2-mercaptoethanol (amount see Table 1) is started and continued at a constant flow rate for 6:00 h. After the feed is completed, the reaction mixture is stirred at 80 °C for 2 h. The remaining amount of the initiator solution is added within 1 h, and the mixture is stirred at 80 °C for 1 h after the feed is completely added. The polymer solution is heated to 110 °C and steam distilled for 2 h to remove volatiles. Demineralized water can be added to adjust the desired solid content.

[0691] Table 1. Amounts of tert-butyl peroxypivalate and 2-mercaptoethanol used in Examples 1, 2, 4, 5, 9, 10 of the present invention.

[0692] tert - Butyl peroxyneopentanoate [g] 2 - Mercaptoethanol [g] Example 1 of the present invention Example 2 of the present invention 2.3 0.50 Example 4 of the present invention 3.4 0.57 Example 5 of the present invention 2.7 0.57 Example 9 of the present invention 2.2 0.47 Example 10 of the present invention 2.2 0.47 Example 2.2 0.47

[0693] Graft polymer - General synthesis according to method (b)

[0694] First, charge 100 g of the main chain (see Table 3) into a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere and heat to 90 °C. The initiator tert-butyl peroxy-2-ethylhexanoate (amount see Table 2) is dosed as a 17 wt% solution in tripropylene glycol at a constant flow rate starting for 6:10 h. After 0:10 h, the feed of vinylimidazole, vinylpyrrolidone, and vinyl acetate is started and continued at a constant flow rate for 6:00 h. After the feed is completed, the remaining amount of the initiator solution is added within 0:56 h and the reaction mixture is stirred at 90 °C for 1 h. Vacuum distillation is carried out at 90 °C and 40 mbar for 2 h to remove volatile components. Demineralized water can be added to adjust the desired solid content.

[0695] Table 2. Amounts of tert-butyl peroxy-2-ethylhexanoate for Examples 3, 6, 7, 8 of the present invention.

[0696] tert - Butyl peroxy - 2 - ethylhexanoate [g] Example 3 of the present invention Example 6 of the present invention 1.8 Example 7 of the present invention 2.0 Example 8 of the present invention 1.7 Description symbol of oxidized PEG 1.5

[0697] Table 3. Examples of the present invention.

[0698]

[0699] VAc = vinyl acetate; VI = vinylimidazole; VP = vinylpyrrolidone.

[0700] (Note: In case of deviation between the main chain description in the table and the synthesis description hereinafter, the following description shall prevail.)

[0701] *) Although not of the present invention due to the definition of the monomers, this graft polymer shows advantages in terms of stability over the - still undisclosed - prior art)

[0702] Example 1

[0703] Example 1a: Polyethylene glycol ethoxylated with 47.2 moles of ethylene oxide (molecular weight 600 g / mol)

[0704] 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 three times with nitrogen and the mixture was heated to 130 °C. 770.0 g of ethylene oxide was added over 10 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, 990.0 g of a light brown solid (hydroxyl value: 45.8 mg KOH / g) was obtained.

[0705] Example 1b

[0706] Polyethylene glycol ethoxylated with 47.2 moles of ethylene oxide and modified with 10 moles of caprolactone (molecular weight 600 g / mol) (main chain A):

[0707] In a 4-necked vessel equipped with a thermometer, reflux condenser, nitrogen inlet, dropping funnel and 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.

[0708] Add 288.8 g of ε-caprolactone within 15 minutes. Heat the reaction mixture to 160 °C and stir under nitrogen at 160 °C for 12 hours. After cooling to room temperature, 900.0 g of orange oil is obtained. In CDCl3 1 1H-NMR indicates a 99.0% conversion of caprolactone.

[0709] Example 1c (grafted polymer)

[0710] Example 1c (invention 1) was synthesized according to the general method a.

[0711] Example 2 (grafted polymer)

[0712] Example 2 (invention 2) was synthesized according to the general method a.

[0713] Example 3 (grafted polymer)

[0714] Example 3 (invention 3) was synthesized according to the general method b.

[0715] Example 4

[0716] Example 4a:

[0717] Polyethylene glycol (molecular weight 600 g / mol) (main chain B) ethoxylated with 47.2 moles of ethylene oxide and modified with 3 moles of caprolactone

[0718] Place 669.8 g of polyethylene glycol (molecular weight 600 g / mol) ethoxylated with 47.2 moles of ethylene oxide (Example 1a) and 0.8 g of tin(II) ethylhexanoate in a 4-necked flask equipped with a thermometer, reflux condenser, nitrogen inlet, dropping funnel and stirrer, and heat to 80 °C.

[0719] Add 85.6 g of ε-caprolactone within 15 minutes. Heat the reaction mixture to 160 °C and stir under nitrogen at 160 °C for 12 hours. After cooling to room temperature, 746.0 g of orange solid is obtained. In CDCl3 1 1H-NMR indicates a 98.0% conversion of caprolactone.

[0720] Example 4b (grafted polymer)

[0721] Example 4b (invention 4) was synthesized according to the general method a.

[0722] Example 5 (grafted polymer)

[0723] Example 5 (invention 5) was synthesized according to the general method a.

[0724] Example 6 (grafted polymer)

[0725] Example 6 (Invention 6) was synthesized according to General Method b.

[0726] Example 7 (Graft Polymer)

[0727] Example 7 (Invention 7) was synthesized according to General Method b.

[0728] Example 8

[0729] Example 8a:

[0730] Neopentyl glycol modified with 8 moles of caprolactone

[0731] In a 4-necked flask equipped with a thermometer, reflux condenser, nitrogen inlet, dropping funnel and 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 were added within 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. 1H-NMR in CDCl3 1 indicated a 99.0% conversion of caprolactone.

[0732] Example 8b:

[0733] Neopentyl glycol modified with 8 moles of caprolactone and ethoxylated with 46 moles of ethylene oxide (main chain C)

[0734] In a 2 l autoclave, 356.1 g of neopentyl glycol modified with 8 moles of caprolactone (Example 8a) 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 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. 1.1 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.

[0735] Example 8c (Graft Polymer)

[0736] Example 8c (Invention 8) was synthesized according to General Method b.

[0737] Example 9

[0738] Example 9a:

[0739] 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 D)

[0740] In a 2 l autoclave, 300.0 g of neopentyl glycol modified with 8 moles of caprolactone (Example 8a) and 1.8 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 519.6 g of ethylene oxide and 68.5 g of propylene 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. 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.

[0741] Example 9b (graft polymer)

[0742] Example 9b (invention 9) was synthesized according to the general method a.

[0743] Example 10

[0744] Example 10a:

[0745] Neopentyl glycol modified with 2 moles of caprolactone

[0746] In a 4-necked vessel equipped with a thermometer, reflux condenser, nitrogen inlet, dropping funnel and 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. 1 1H-NMR indicated a 99.0% conversion of caprolactone.

[0747] Example 10b:

[0748] Neopentyl glycol modified with 2 moles of caprolactone and ethoxylated with 40 moles of ethylene oxide (main chain E)

[0749] In a 2 l autoclave, 149.6 g of neopentyl glycol modified with 2 moles of caprolactone (Example 10a) 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 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. 1.0 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.

[0750] Example 10c (graft polymer)

[0751] Example 10c (of the present invention 10) was synthesized according to the general method a.

[0752] Example 11 (for comparison of stability)

[0753] Example 11a: Polyethylene glycol ethoxylated with 44 moles of ethylene oxide (molecular weight 1500 g / mol)

[0754] 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 with nitrogen three times and the mixture was heated to 140 °C. 754.2 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. After filtration, 1350.0 g of a light brown solid was obtained. 1H-NMR in CDCl3 confirmed the expected structure.

[0755] Example 11b (main chain F): Polyethylene glycol ethoxylated with 44 moles of ethylene oxide and modified with 6 moles of caprolactone (molecular weight 1500 g / mol)

[0756] In a 4-necked vessel equipped with a thermometer, reflux condenser, nitrogen inlet, dropping funnel and stirrer, 1044.1 g of polyethylene glycol ethoxylated with 44 moles of ethylene oxide (molecular weight 1500 g / mol) (Example 5a) and 1.25 g of tin(II) ethylhexanoate were placed and heated to 90 °C.

[0757] 205.5 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 10 hours. After cooling to room temperature, 1236.0 g of an orange oil was obtained. In 1 H-NMR indicated a 98.8% conversion of caprolactone.

[0758] Example 11c (graft polymer)

[0759] First, charge the main chain F (455.00 g) into a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere and heat to 90 °C. Start 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) 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: 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, meter Feed 3 (1.79 g of tert-butyl peroxy-2-ethylhexanoate dissolved in 15.72 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 745 g of a polymer solution.

[0760] Synthesis of Comparative Examples

[0761] Table 4: Comparative Examples.

[0762]

[0763] 1) Pluronic RPE 1050; 50% EO; PO / EO / PO triblock copolymer; *) hydrolyzed to approximately 40% of the VAc-derived moiety after polymerization

[0764] Synthesis procedure of comparative examples:

[0765] Comparative Example I: Copolymer of N-vinylpyrrolidone and 1-N-vinylimidazole, weight ratio 1:1; K-value approximately 30; available from BASF as Sokalan HP 56, for example.

[0766] Comparative Example II: Preparation of a polymer as described in Example 1 of WO 03 / 042264.

[0767] Comparative Example III:

[0768] Initially, in a nitrogen atmosphere, PEG (288.00 g) and water (629.00 g) were charged into a polymerization vessel equipped with a stirrer and a reflux condenser and heated to 80 °C. At the same time, Feed 1 (96.00 g of vinylimidazole and 96.00 g of vinylpyrrolidone), Feed 2 (3.20 g of tert-butyl peroxyneopentanoate dissolved in 71.81 g of isopropanol), and Feed 3 (1.92 g of 2-mercaptoethanol in 98.08 g of water) were started and metered into the stirred vessel at a constant feed rate over Feed 1 (6:00 h), Feed 2 (6:30 h), and Feed 3 (6:00 h). After the feeding was completed, the mixture was stirred at 80 °C for 2:00 h. Feed 4 (1.28 g of tert-butyl peroxyneopentanoate dissolved in 28.70 g of isopropanol) was metered in at 80 °C at a constant feed rate over 1:00 h. After the complete addition of the feed, the mixture was stirred at 80 °C for 1:00 h. The polymerization mixture was diluted with 400 g of water and heated to 100 °C. Steam distillation was carried out at 100 °C for 1:00 h to remove volatiles. The yield was 1213 g of a polymer solution.

[0769] Comparative Example IV:

[0770] Initially, in a nitrogen atmosphere, a random EO / PO copolymer (288.00 g) and water (386.00 g) were charged into a polymerization vessel equipped with a stirrer and a reflux condenser and heated to 80 °C. At the same time, Feed 1 (96.00 g of vinylimidazole and 96.00 g of vinylpyrrolidone), Feed 2 (3.20 g of tert-butyl peroxyneopentanoate dissolved in 71.81 g of isopropanol), and Feed 3 (1.92 g of 2-mercaptoethanol in 98.08 g of water) were started and metered into the stirred vessel at a constant feed rate over Feed 1 (6:00 h), Feed 2 (6:30 h), and Feed 3 (6:00 h). After the feeding was completed, the mixture was stirred at 80 °C for 2:00 h. Feed 4 (1.28 g of tert-butyl peroxyneopentanoate dissolved in 28.70 g of isopropanol) was metered in at 80 °C at a constant feed rate over 1:00 h. After the complete addition of the feed, the mixture was stirred at 80 °C for 1:00 h. The polymerization mixture was diluted with 600 g of water and heated to 100 °C. Steam distillation was carried out at 100 °C for 1:00 h to remove volatiles. The yield was 1813 g of a polymer solution.

[0771] Comparative Example V:

[0772] Initially, PEG (312.00 g) and water (312.00 g) were charged into a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere and heated to 80 °C. Feed 2 (9.60 g of tert-butyl peroxypivalate dissolved in 21.91 g of tripropylene glycol) was started, and 10 min after the start of Feed 2, Feed 1 (96.00 g of vinylimidazole and 72.00 g of vinylpyrrolidone) and Feed 3 (1.92 g of 2-mercaptoethanol in 98.06 g of water) were started simultaneously. All feeds were metered into the stirred vessel at a constant feed rate within Feed 1 (6:00 h), Feed 2 (6:40 h), and Feed 3 (6:00 h). After the feeding was completed, the mixture was stirred at 80 °C for 2:00 h. Feed 4 (5.12 g of tert-butyl peroxypivalate dissolved in 11.69 g of tripropylene glycol) was metered into the mixture at a constant feed rate at 80 °C within 1:00 h. After the complete addition of the feeds, the mixture was stirred at 80 °C for 1:00 h. Water (268.10 g) was added and the polymerization mixture was heated to 100 °C. Steam distillation was carried out at 100 °C for 1:00 h to remove volatiles. The yield was 1232 g of a polymer solution.

[0773] Comparative Example VI:

[0774] Initially, an EO / PO random copolymer (240.00 g) and water (240.00 g) were charged into a polymerization vessel equipped with a stirrer and a reflux condenser under a nitrogen atmosphere and heated to 80 °C. Feed 2 (9.60 g of tert-butyl peroxypivalate dissolved in 21.91 g of tripropylene glycol) was started, and 10 min after the start of Feed 2, Feed 1 (120.00 g of vinylimidazole and 120.00 g of vinylpyrrolidone) and Feed 3 (1.92 g of 2-mercaptoethanol in 122.06 g of water) were started simultaneously. All feeds were metered into the stirred vessel at a constant feed rate within Feed 1 (6:00 h), Feed 2 (6:40 h), and Feed 3 (6:00 h). After the feeding was completed, the mixture was stirred at 80 °C for 2:00 h. Feed 4 (5.12 g of tert-butyl peroxypivalate dissolved in 11.69 g of tripropylene glycol) was metered into the mixture at a constant feed rate at 80 °C within 1:00 h. After the complete addition of the feeds, the mixture was stirred at 80 °C for 1:00 h. Water (340.10 g) was added and the polymerization mixture was heated to 100 °C. Steam distillation was carried out at 100 °C for 1:00 h to remove volatiles. The yield was 1232 g of a polymer solution.

[0775] Synthesis of Comparative Example VII:

[0776] A polymer was prepared as described in Example 1K of US2019 / 0390142 A1.

[0777] Synthesis of graft polymer comparative example VIII:

[0778] (According to the disclosure of unpublished patent application PCT / EP 2022 / 065983)

[0779] Synthesized in the following three-step procedure:

[0780] Step 1: Oxidation of PAG

[0781] Oxidize a polyalkylene oxide having two primary OH end groups (referred to as "diol") into a mixture of at least a polyalkylene oxide having two COOH end groups (referred to as "diacid"), a polyalkylene oxide having one primary OH and one COOH end group (referred to as "monoacid"), and, optionally, a polyalkylene oxide having two primary OH end groups is also retained. The mixture is prepared as follows.

[0782] Suspend platinum / carbon (5.0 wt.-% Pt / C, water content: 59.7 wt.-%, 283 g, 29.2 mmol Pt) in a mixture of a polyalkylene oxide having two primary OH end groups (details see Table 1) and water (details see Table 1), heat to 52 °C and stir at 800 rpm. Pass oxygen through the stirred mixture (20 nL / h) via a glass tube equipped with a fritted disc and allow the temperature to rise to 60 °C. Maintain the oxygen dosage and temperature for the period mentioned in Table 1, then stop the oxygen dosage and allow the mixture to cool to room temperature. Separate the solid from the liquid phase by filtration, and wash the filter cake with 500 mL of warm water. Mix the wash water with the filtrate. Remove water 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).

[0783] Polymer backbone - Table 1 - Oxidation of PEG

[0784] EO600 A1 A2 <![CDATA[Type of polyalkylene oxide #1 and the average molecular weight M w [g / mol]]]> EO600 The number average value of the number of ether groups Amount of polyalkylene oxide [g] 12 12 Amount of water [g] 1500 1750 Oxidation time [h] 3500 4083 Acid value [mg KOH / g] 72 8 <![CDATA[Ratio of oxidized OH groups [%] #2 > <![CDATA[>99 #2 > <![CDATA[51 #2 > Physical properties 55 28 Solid Solid Figure 1

[0785] #1 EO = polyethylene oxide

[0786] #2 Calculated based on the acid value of the reaction solution

[0787] Step 2: Esterification

[0788] Mix the mixture of polyalkylene oxides obtained by the oxidation of diol (see Table 1) (see Table 2) and an esterification catalyst (see Table 2) and heat under vacuum at a pressure of 1 kPa absolute at a temperature of 135 °C for the period mentioned in Table 2.

[0789] Table 2 - Esterification to PEG-esters

[0790]

[0791] Notes on the polymer backbone - Table 2:

[0792] #1 Catalyst = Zinc octanoate

[0793] #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 specific polymer increases, the K-value also tends to increase. The K-value is determined at 23 °C in a polymer concentration of 3% NaCl solution by weight and 1% polymer according to the method of H. Fikentscher in "Cellulosechemie [Cellulose Chemistry]", 1932, 13, 58.

[0794] Step 3: Synthesis of graft polymer 1 for comparison

[0795] 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 tert-butyl peroxy-2-ethylhexanoate in tripropylene glycol (1.00 g) 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 LN2 / h for 90 minutes.

[0796] Stability of the graft polymer on the backbone *) of the present invention relative to the comparative graft polymer

[0797] (*) Although outside the monomer definition and thus "not of the present invention" per se)

[0798] Aqueous solutions of the graft polymer 11 of the present invention and the comparative polymer 1 (9 wt%) were prepared, and the mixture was stored at 54 °C for two weeks.

[0799] During the storage of the comparative graft polymer 1, a brown precipitate formed. The recorded precipitate and solution 1 1H NMR (298 K, D2O, 400 MHz) spectra showed no differences. Comparison of the 1H NMR spectra of fresh and stored samples of the comparative graft polymer 1 showed1 A significant rearrangement in the region of the 1H NMR shift at 4.0 to 4.35 ppm (typical for the PEG-ester bond) and 1.8 to 2.2 ppm (typical for the bound / unbound acetate), as Figure 2 shown in

[0800] A comparison of the 1H NMR spectra (298K, D2O, 400 MHz) of fresh and stored samples of the graft polymer (invention 5 of the present invention) shows no significant rearrangement in the spectra as 1 shown in Evaluation of DTI performance (laundry experiment) shown.

[0801] These results clearly show better hydrolysis instability of the polymer based on the backbone of the present invention.

[0802] Performance testing of the graft polymer

[0803] The performance evaluation of the graft polymer can be obtained through clothing experiments and cleaning experiments. The clothing experiments can be carried out in a washing machine or alternatively in a device to conduct model clothing experiments such as a Launderometer or a Tergotometer.

[0804] Ingredients

[0805] Washing results:

[0806] Selected colored fabrics (EMPA 130 and EMPA 133 as dye donors) are washed at 60 °C in the presence of white test fabrics and polyester ballast fabrics with the addition of a dye transfer inhibitor. The liquid detergent is based on a mixture of anionic and non-ionic surfactants (LAS; AES, AEO). After the washing cycle, the fabrics are rinsed, spun, and dried. To determine the dye transfer inhibition effect, the staining of the white test fabrics is determined photometrically. The color values in L*a*b are determined using a Colour Consult b.v., Mach 5+, camera-based multi-spectral color measurement instrument. The color shift is calculated as ΔΔE.

[0807] Composition of the liquid detergent ("ES1_C")

[0808] [% by weight] Linear dodecylbenzenesulfonic acid C12C14 fatty alcohol ether sulfate, Na salt 5.5 C13C15 oxo - synthesis alcohol having 7 EO 5.4 Coconut fatty acid K12 - 18 5.4 1,2 - propylene glycol 2.4 Ethanol 6.0 NaOH 2.0 Sodium citrate 2.2 DTI additive 3.0 Active material of 0.5 / 1.0 Water Made up to 100 ​

[0809] DTI-additive / DTI polymer = at least one graft polymer of the present invention

[0810] Washing conditions

[0811]

[0812] Explanation of abbreviations in the previous table:

[0813] wfk 10A: Cotton fabric

[0814] wfk 20A: Polyester-cotton fabric

[0815] EMPA 130: Cotton fabric dyed with Direct Red 83.1

[0816] EMPA 133: Cotton fabric dyed with Direct Blue 71

[0817] Washing results of EMPA 130 colored fabric (red) (evaluation, calculated as ΔΔE = ΔE(without) - ΔE(polymer))

[0818]

[0819] Washing results of EMPA 133 colored fabric (blue) (evaluation, calculated as ΔΔE = ΔE(without) - ΔE(polymer))

[0820]

[0821]

[0822] For comparative polymers, Comparative Example I to Comparative Example VI - Another set of washing examples

[0823] In the presence of a dye transfer inhibitor, the selected colored fabrics (EMPA 130 and EMPA 133 as dye donors) are washed at 60 °C in the presence of a white test fabric and a polyester ballast fabric. The liquid detergent is based on a mixture of anionic and non-ionic surfactants (LAS; AES, AEO). After the washing cycle, the fabrics are rinsed, spun, and dried. To determine the dye transfer inhibition effect, the staining of the white test fabric is determined photometrically. The reflectance is determined at 520 nm (EMPA 130) or at 600 nm (EMPA 133) using a Datacolor photometer (Elrepho 2000).

[0824] Composition of the liquid detergent

[0825]

[0826]

[0827] Washing conditions

[0828]

[0829] Explanation of abbreviations in the previous table:

[0830] wfk 10A: Cotton fabric, reflectance 83.4% (520 nm), 84.5% (600 nm)

[0831] wfk 20A: Polyester-cotton fabric, reflectance 83.8% (520 nm), 83.3% (600 nm)

[0832] EMPA 130: Cotton fabric dyed with Direct Red 83.1

[0833] EMPA 133: Cotton fabric dyed with Direct Blue 71

[0834] Manufacturer / supplier: wfk Testgewebe GmbH, Brugg, Germany; EMPA Testmaterialien AG, St. Gallen, Switzerland

[0835] Washing results of EMPA 130 and EMPA 133 coloured fabrics (evaluated % reflectance)

[0836] Washing results of EMPA 130 and EMPA 133 coloured fabrics (evaluated % reflectance)

[0837]

Claims

1. A graft polymer, which consists of the following: (A) 20% to 95%, preferably 50% to 90%, more preferably 60% to 90%, even more preferably 65% to 85%, most preferably 70% to 85% of a polymer backbone as a graft matrix, The polymer backbone contains at least one subunit (a1) and at least one subunit (a2), wherein (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, 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, wherein preferably the at least one lactone and / or hydroxy - acid is selected from group i) and / or ii), wherein 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; 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, wherein the polymer backbone a) is obtained by: (A1) Copolymerization of at least one subunit (a1) and at least one subunit (a2), wherein 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 at least one subunit (a1) and at least one subunit (a2); (A2) First oligomerizing / polymerizing the subunit (a2), and then polymerizing the product with the subunit (a1); (A3) First oligomerizing / polymerizing the subunit (a1), and then copolymerizing 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 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 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 employed oligomer or polymer, 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 obtained 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 more than one subunit (a1) and / or more than one subunit (a2) are present; (A2) A main chain composed of an oligomeric subunit or a polymeric subunit (a2) as an 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 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.; (A3) A main chain composed of an internal block of oligomeric and / or polymeric (a1)-subunits and two external 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 an opposite end of the first block via an ether or ester functional group (opposite to the capping group on the first block), the second block being composed of at least one subunit (a2) and optionally at least one subunit (a1), 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 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 when only using subunit (a2) for the second block: [capping group]-[subunit (a1)]-[subunit (a2)] Or has the following as an idealized structure when using subunits (a1) and (a2) for the second block: [capping group]-[subunit (a1)]-[random-{subunit (a2)-subunit (a1)}]; and wherein in the case of (A1), (A2) and (A3), the use of starting molecules is optional; and (B) 5% to 80%, preferably 10% to 50%, more preferably 10% to 40%, even more preferably 15% to 35% and most preferably 15% to 30% of polymer side chains (B) grafted onto the polymer backbone (A), wherein the polymer side chains (B) are obtainable by (co)polymerization of: optionally (B1) at least one vinyl ester monomer, at least one, preferably at least two nitrogen-containing monomers (B2), and optionally additional monomers (B3), and optionally additional monomers, wherein 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 to prepare the backbone / are present in the backbone.

3. The graft polymer according to claims 1 to 2, wherein These monomers are selected from: (B1) optionally 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; (B2) At least one, preferably at least two nitrogen-containing monomers 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(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-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 (B) is 10% to 40%, more preferably 15% to 35% and most preferably 15% to 30%; The amount of (B1) (vinyl ester), by weight percentage based on the total weight of the graft polymer, is 0% to 20%, preferably up to 15%, more preferably up to 10%, even more preferably up to 5%; The amount of (B2) (nitrogen-containing monomer), by weight percentage based on the total weight of the graft polymer, is 10% to 40%, preferably up to 35%, more preferably up to 30%, even more preferably up to 25% and most preferably up to 20% and more preferably at least 15%, and - more preferably - the amount of (B2a) vinyl imidazole monomer, preferably N-vinylimidazole, is 20% to 80%, preferably 30% to 70%, most preferably 40% to 60%, each by weight percentage based on the total weight of (B2); and the amount of (B2b) vinyl lactam monomer, preferably N-vinylpyrrolidone, is equal to [(the total amount of (B2) minus (B2a))]; And further on the premise that (B3) (additional monomer) is 0 wt.% to 5 wt.%, preferably at most 2 wt.%, more preferably at most 1 wt.%, even more preferably about 0 wt.%, but in all cases at most 10 wt.% of the amount of (B2), based on the total weight of the graft polymer.

5. The graft polymer according to any one of claims 1 to 4, wherein, At least 10 weight percent of the total amount of the optional 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 comprises moieties derived from: (i) An alkylene oxide (AO) comprising 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 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 backbone, 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, 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 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) 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 / 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 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) is 15% to 30%; and these monomers: (B1) (vinyl ester) is absent (B2) (nitrogen-containing monomer) is (B2a) N-vinylimidazole, which is 40% to 60% by weight percentage based on the total weight of (B2); and (B2b) N-vinylpyrrolidone, equal to [(the total amount of (B2) minus (B2a))]; (B3) and other monomers are substantially absent.

10. The graft polymer according to any one of claims 1 to 8, wherein, (B) is 15% to 30%; and these monomers: (B1) Vinyl acetate is 5% to 10% by weight percentage based on the total weight of the graft polymer; (B2) (nitrogen-containing monomer), by weight percentage based on the total weight of the graft polymer, is 10% to 25%, wherein (B2a) N-vinylimidazole is 40% to 60% by weight percentage based on the total weight of (B2); and (B2b) Vinyl lactam - monomer, preferably N-vinylpyrrolidone, equal to [(the total amount of (B2) minus (B2a))]; (B3) and other monomers are substantially absent.

11. The graft polymer according to any one of claims 1 to 10, wherein, wherein at least one of the following i), ii) and iii) is satisfied: i) These polymer backbones (A1), (A2), and (A3) can carry two hydroxyl groups as end groups or can be capped with C1 to C22-alkyl, preferably C1 to C4 alkyl; after the final preparation of the backbone, such end groups are attached using standard means, while for (A4), such capping is carried out on the oligomeric / polymeric subunit (a1) before the polycondensation with 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, as well as 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., as well as any value therebetween and up to 100%.

12. A method for obtaining a graft polymer according to any one of claims 1 to 11, the method comprising the following steps: Optionally, at least one vinyl ester monomer (B1), at least one, preferably at least two nitrogen-containing monomers (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), where these polymer side chains (B) are obtained by radical polymerization, preferably using a radical-forming compound to initiate the radical polymerization.

13. The method according to claim 12, which comprises polymerizing these monomers (B) in the presence of at least one polymer backbone (A) - preferably selected from backbones (A1), (A2), (A3) and (A4), a free-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 optionally (B1), (B2) and optionally (B3) and the initiator (C) in the reaction mixture remain continuously quantitatively deficient relative to the polymer backbone (A), where - if (B1) is used - 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 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 percentages based on the total weight of the vinyl ester monomer B1 used), and - preferably - the amounts of the monomers are those as described in any one of the claims listing such amounts as previously, and where these monomers and amounts are preferably those of claim 9 or 10.

14. The method according to any one of claims 12 or 13, 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.

15. The method according to any one of claims 12 to 14, wherein The method comprises at least one further method step selected from the following: i) A post-polymerization method step, which is carried out after the main polymerization reaction, where preferably an additional amount of initiator (optionally dissolved in the solvent) is added over a period of 0.5 hour and up to 3 hours, preferably about 1 to 2 hours, more preferably about 1 hour, where 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 is allowed to continue, and then the post-polymerization reaction is started by starting to add additional free-radical initiator, such a period of time being 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 method 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 higher, preferably 10 °C to 20 °C higher; ii) subjecting the graft polymer obtained, e.g., from the main polymerization or - if carried out - from the post-polymerization method step, to means for purification, concentration, and / or drying to remove some or almost all of the remaining solvents (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 applying stripping with a gas such as steam or an inert gas such as nitrogen, preferably using steam from water, to remove some 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 solvents and / or unreacted monomers, 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 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.

16. The method according to any one of claims 12 to 15, 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).

17. Use of at least one graft polymer according to any one of claims 1 to 11 or obtainable or obtained by a method according to any one of claims 12 to 16 in a composition which is a fabric and home care product, a cleaning composition, an industrial and institutional cleaning product.

18. Use according to claim 17, 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, the cleaning composition preferably being a laundry detergent formulation, and more preferably the graft polymer is used as a dye transfer inhibitor, optionally further comprising at least one enzyme, the at least one enzyme preferably being 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 being 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 from about 1% to about 70% by weight of a surfactant system.

19. A composition which is a fabric and home care product, a cleaning composition, an industrial and institutional cleaning product, preferably a laundry detergent, which contains at least one graft polymer as claimed in any one of claims 1 to 11 or obtainable or obtained by a method as claimed in any one of claims 12 to 16, the graft polymer is preferably used as a dye transfer inhibitor, optionally further comprising 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, 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 0.05% to 10%, more preferably from about 0.1% to 8%, even more preferably from about 0.2% to about 6% and further 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, and such product or composition further comprises from about 1% to about 70% by weight of a surfactant system.

20. The composition according to claim 19, which further comprises 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% of phenoxyethanol.

21. The composition according to claim 19 or 20, which comprises 4,4'-dichloro-2-hydroxy diphenyl ether at a concentration of 0.001% to 3%, preferably 0.002% to 1%, more preferably 0.01% to 0.6% - each based on the weight of the composition.

22. A method of preserving the composition according to any one of claims 19 or 21 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.

23. A method for washing fabrics or cleaning hard surfaces, the method comprising treating the fabrics or hard surfaces with a composition according to claim 19 or 20, wherein, The composition comprises 4,4'-dichloro-2-hydroxy diphenyl ether, preferably comprising 4,4'-dichloro-2-hydroxy diphenyl ether at a concentration of 0.001% to 3%, preferably 0.002% to 1%, more preferably 0.01% to 0.6% - each based on the weight of the composition.

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